Spatially controlled functionality of polymeric products

ABSTRACT

Functional and/or functional precursor products, formulations for making the products, methods of making the products (e.g. functional coatings, concentrated gradients, and/or composites), and uses thereof are provided. In an aspect, the method comprises a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of, and priority from, the following applications, all of which applications are incorporated herein by reference in their entirety: U.S. Provisional Patent Application No. 62/895,218, filed on Sep. 3, 2019; U.S. Provisional Patent Application No. 62/923,136, filed on Oct. 18, 2019; U.S. Provisional Patent Application No. 62/923,103, filed on Oct. 18, 2019; U.S. Provisional Patent Application No. 62/923,043, filed on Oct. 18, 2019; and PCT Patent Application PCT/IB2019/058923, filed on Oct. 18, 2019.

FIELD

The disclosure relates to functional and/or functional precursor products, formulations for making the products, methods of making the products, and uses thereof.

BACKGROUND

Functional products are products that perform at least one function. In the traditional sense, it would encompass a product that has, for example, one or more chemical, mechanical, magnetic, thermal, electrical, optical, electrochemical, protective, and catalytic properties. It could also, or instead, include a product that has an aesthetically pleasing property.

3D printing is an emerging technology poised to transform manufacturing of functional products. A challenge faced with 3D printing, in general, is the availability of feedstock materials, particularly for functional products. Stereolithographic (SLA) printing is one of a number of 3D printing techniques that faces this problem. The bulk of the feedstock materials are based on polymer resins and as a result the technique is limited to generating products with basic function (e.g. structural). New formulations that incorporate functionality would allow a 3D printing technique to generate structural components with specific functions (e.g. electrical conduction).

At present, most methods use multi-steps and lengthy processes to generate, for example, conductive 3D printed structures. For instance, 3D printed elastomeric structures were formed by digital light processing (DLP), once printed and processed, the structure is subsequently immersed in a solution of silver nanoparticles and exposed to hydrogen chloride vapors. (Magdassi, S. et al., Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3D Printing, Adv. Mater. 2017, 29, 1606000).

A polymer based ink was developed that prints a porous structure. The porous structure was put under vacuum and dipped in a dispersion of silver nanoparticles. The structure was then sintered. (Magdassi, S. et al., 3D Printing of Porous Structures by UV-curable O/W Emulsion for Fabrication of Conductive Objects, J. Mater Chem. C. 2015, 3, 2040).

The drawbacks of available 3D printing feedstock materials (e.g. resin or filament) is that the materials require multiple and lengthy steps post-printing to generate, for example, a functional 3D structure and, for example, especially selective positioning of functionality in a 3D structure.

The background herein is included solely to explain the context of the disclosure. This is not to be taken as an admission that any of the material referred to was published, known, or part of the common general knowledge as of the priority date.

SUMMARY

In an aspect, there is provided a method for making a product, the method comprising: a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one second polymerizable component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a formulation for making a product, the formulation comprising a composition having at least one first polymerizable component and at least one second polymerizable component, the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a method for making a product, the method comprising a) polymerizing at least one first polymerizable component to form at least one first polymer structure; b) combining the at least one first polymer structure and at least one first component, wherein the at least one first component comprises at least one functional component, at least one functional precursor component, or combinations thereof, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one first component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a method for making a product, the method comprising: a) combining at least one first polymerizable component and at least one polymer and/or polymer derivative to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one polymer and/or polymer derivative, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one at least one polymer and/or polymer derivative, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another aspect, there is provided a formulation for making a product, the formulation comprising a composition having at least one first polymerizable component and at least one at least one polymer and/or polymer derivative, the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one at least one polymer and/or polymer derivative, and the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

It is understood that one or more of the aspects described herein (and above) may be combined in any suitable manner. It should be understood that the detailed description and the specific examples presented, while indicating certain aspects, are provided for illustration purposes only because various changes and modifications within the spirit and scope will become apparent to those of skill in the art from the detailed description and claims that follow.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are described in detail below with reference to the Figures, wherein:

FIG. 1 shows a schematic of some embodiments of a method.

FIGS. 2A, 2B, and 2C show examples of 3D printed products. The formulations used to make these products are described in Examples 1-15.

FIGS. 3A-3D shows scanning electron microscope (SEM) images of examples of 3D printed cylinders (FIGS. 3A-3C) and a perspective view (FIG. 3D) of where the SEM images were taken on the cylinders (see circle). The formulation used to make these cylinders is described in Example 4.

FIGS. 4A and 4B show cross-sectional SEM images of the interface of an example of a 3D printed product.

FIG. 5 shows thermal gravimetric analysis (TGA) of silver SLA 3D product cured in air. The formulation used to make this product is described in Example 5.

FIGS. 6A and 6B show optical images of a 5 μL drop of water on a 3D printed tile containing a) 0 wt. %, and b) 20 wt. % respectively of 1H,1H-perfluorooctyl methacrylate. The formulation used to make this product is described in Example 15.

FIG. 7 shows a graph of contact angles of 3D printed tiles and of UV-cured films vs. % wt. fluorinated methacrylate monomer. The formulation used to make this product is described in Example 15.

FIG. 8 shows the surface concentration of silver of 3D printed products made from resins with varying amounts of cross-linking agents. The formulations used to make these products are described in Examples 16-26 and 31-41.

FIG. 9 shows the resistance of the silver coating on 3D printed products made from resins with varying amounts of cross-linking agents. The formulations used to make these products are described in Examples 16-26 and 31-41.

FIG. 10 shows the concentration of silver within a 3D printed cylinder. For samples made with 20-35% EGDA, a silver coating can form where the concentration of silver decreases with increased distance from the surface of the cylinder. For the sample made with 99% EDGA, the silver concentrations are substantially uniform across the cross-section of the product.

FIG. 11 shows SEM images and schematic of a strain sensor made from a 3D printed product. The 3D silver product was prepared using the resin composition described in Example 54. As the strain sensor is compressed, the silver nanoparticles made contact and increased the conductivity of the silver film.

FIG. 12 shows the results of a cycling experiment where the electrical resistance of a 3D printed strain sensor was compressed by various length scales. As the sample is compressed, the resistance drops. The 3D silver product was prepared using the formulation described in Example 54.

FIG. 13 shows representative photographs of the bacterial inhibition zones created by the different scaffolds against E. coli. E. coli was plated on LB agar at ˜1×109 cfu/ml, 18 hr growth. The 3D products were prepared using the formulation described in Example 57.

FIG. 14 shows representative photographs of antibacterial performance of different scaffolds against TG1 (E. coli). 24 hr growth of TG1 with 3D silver products and control product. The 3D silver products were prepared using the formulation described in Example 57.

FIG. 15 shows a growth curve of E. coli TG1 with 3D silver products and control product. The 3D silver products were prepared using the formulation described in Example 57.

FIG. 16 shows a growth curve of E. coli TG1 with broth of silver product supernatant (42 hr). The 3D silver products were prepared using the formulation described in Example 57.

FIG. 17 shows SEM images of 3D TiO₂ products printed without toluene (a, b and c) and with toluene (d, e and f). The 3D TiO₂ products were prepared using the formulations described in Examples 50 and 51.

FIG. 18 shows wt % of TiO₂ as a function of distance from the surface of the 3D TiO₂ products. The 3D TiO₂ products were prepared using the formulations described in Examples 50 and 51.

FIG. 19 shows SEM images of 3D Barium Strontium Titanate (BST) product. The 3D BST product was prepared using the formulation described in Example 52.

FIG. 20 shows a) SEM images of the cross-section of a printed cylinder with iron oxide nanoparticles. The nanoparticles appear as bright areas in the SEM; energy dispersion spectroscopy (EDS) analysis of the SEM mapping out b) carbon and c) iron in the sample. The 3D iron product was prepared using the formulation described in Example 53.

FIG. 21 shows the contact angle of 3D printed tiles printed using photoresins with three different fluorinated monomers. The 3D printed tiles were prepared using the formulation described in Example 58.

FIG. 22 shows the contact angle of 3D printed tiles, printed using 20% wt. 2,2,3,4,4,4-hexafluorobutyl methacrylate, as a function of depth of the tile. The 3D printed tiles were prepared using the formulation described in Example 58.

FIG. 23 shows an example of vat polymerization 3D printing.

FIG. 24 shows an example of photopolymerization induced phase separation (PIPS) for controlled placement of functionality in a 3D printed product.

FIG. 25 shows another example of photopolymerization induced phase separation (PIPS) for controlled placement of functionality in another 3D printed product.

FIG. 26 shows (a) Computer aided design (CAD) image of hexagonal patterned sheets with “spaces” in between the individual hexagons and sheets of hexagons. (b) and (c) Scanning electron microscope (SEM) with a backscatter electron detector (BSE) images of commercial Form Labs Ceramic resin 3D printed in hexagonal design structure. The image on the bottom left (b) shows the hexagonal pattern (area denoted by reference numeral 1) with a border (areas denoted by reference numerals 2 and 3) and spaces in between (area denoted by reference numeral 4). The particle density (the four images on the right in (c)) changes based on the location in and around the hexagons with less particles at reference numeral 3 along the hexagonal border compared to the actual hexagonal shape and spaces in between (reference numerals 1, 2, and 4). The 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60a.

FIG. 27 shows (a) Computer-aided design (CAD) image of hexagonal 3D printed platelets/sheets with “spaces” in between and support bridges to hold the individual platelets/sheets together. (b) and (c) Microscope images of 3D printed structure with one photopolymer (ethylene glycol phenyl ether acrylate:1,6 hexanediol diacrylate) and one functional material (hydride terminated polydimethylsiloxane). The hexagonal platelets and spaces both contain cured polymer, but the spaces are more transparent while the platelets are opaque due to the phase separated polydimethylsiloxane functional material. The 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60b.

FIG. 28 shows (a) Scanning electron microscope (SEM) images of the cross-section of ethylene glycol phenyl ether acrylate:1,6-hexanediol diacrylate photopolymer with phase separated hydride terminated polydimethylsiloxane. (b) and (c) Energy dispersive X-ray spectroscopy (EDS) line spectrum of the cross-section showing a variation in elemental Si from the hydride terminated polydimethylsiloxane across the opaque hexagon platelets and transparent spaces. In (b), the upper line represents C, the mid-line Si and the bottom line O. (c) shows Si at a more granular cps scale. The 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60b.

FIG. 29 shows scanning electron microscope (SEM) images of the cross-section of ethylene glycol phenyl ether acrylate:1,6-hexanediol diacrylate photopolymer with phase separated hydride terminated polydimethylsiloxane. The 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60b.

FIG. 30 shows a-d) top and e-f) side images of the custom designed structure of example platelets separated by spaces and held together with support bridges using a stereolithographic printer. a, c, and e) show the structure after printing and before infiltration with the thermal curable resin. b, d, f) show the structure after infiltration and thermal curing of the second resin. The 3D printed structure and infiltration methods are described in Example 59a.

FIG. 31 shows a) Image of an example structure with bottom of the structure transparent and top dyed darker with the color of the second photoinitiator and co-initiator. b) Raman spectroscopy mapping at the interface between the top and bottom of the structure in a) with respect to the change in —C—H peak intensity relative to the baseline at ˜2920 cm⁻¹. The method is described in Example 62a.

DETAILED DESCRIPTION OF CERTAIN ASPECTS Definitions

Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the present invention, the typical materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used.

It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. Patent applications, patents, and publications are cited herein to assist in understanding the aspects described. All such references cited herein are incorporated herein by reference in their entirety and for all purposes to the same extent as if each individual publication or patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety for all purposes. To the extent publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to supersede and/or take precedence over any such contradictory material.

In understanding the scope of the present application, the articles “a”, “an”, “the”, and “said” are intended to mean that there are one or more of the elements. Additionally, the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives.

It will be understood that any aspects described as “comprising” certain components may also “consist of” or “consist essentially of,” wherein “consisting of” has a closed-ended or restrictive meaning and “consisting essentially of” means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention. For example, a composition defined using the phrase “consisting essentially of” encompasses any known acceptable additive, excipient, diluent, carrier, and the like. Typically, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1%, and even more typically less than 0.1% by weight of non-specified component(s).

It will be understood that any component defined herein as being included may be explicitly excluded from the claimed invention by way of proviso or negative limitation.

In addition, all ranges given herein include the end of the ranges and also any intermediate range points, whether explicitly stated or not.

Terms of degree such as “substantially”, “about” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.

The abbreviation, “e.g.” is derived from the Latin exempli gratia, and is used herein to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example.” The word “or” is intended to include “and” unless the context clearly indicates otherwise.

The phrase “at least one of” is understood to be one or more. The phrase “at least one of . . . and . . . ” is understood to mean at least one of the elements listed or a combination thereof, if not explicitly listed. For example, “at least one of A, B, and C” is understood to mean A alone or B alone or C alone or a combination of A and B or a combination of A and C or a combination of B and C or a combination of A, B, and C. “At least one of at least one of A, at least one of B, and at least one of C” is understood to mean at least one of A alone or at least one of B alone or at least one of C alone or a combination of at least one of A and at least one of B or a combination of at least one of A and at least one of C or a combination of at least one of B and at least one of C or a combination of at least one of A, at least one of B, and at least one of C.

The term “composition” is understood to mean having two or more components/elements.

The term “a substantially homogeneous mixture” is understood to mean a substantially uniform mixture or combination of components.

The term “morphology” is understood to mean a shape and size of an area or a volume (e.g. the texture or topography of a surface; the habit of a crystal; the distribution of phases in a material).

The term “phase” is interchangeably used herein with “morphology”, “layer”, “zone”, and/or “structure”. These terms are understood to mean a region of a functional product and/or a functional precursor product having an area or volume of material with relatively uniform chemical and/or physical properties. For example, one phase or region may have uniform chemical and/or physical properties and another phase or region may have different uniform chemical and/or physical properties. It is understood that a given phase or region having relatively uniform chemical and/or physical properties can, but does not necessarily require, homogeneity throughout the phase. An interface between phases may also constitute a distinct phase. For example, a phase may have a component present in amounts falling within a desired concentration range. Alternatively, there may be a variation in the degree of polymer cross-linking in a phase to provide a desired level of flexibility, rigidity or other property to a functional product. Phases may arise from printing using distinct formulations, in sequence, to produce distinct regions, or may arise out of polymerization processes designed to result in product component phase separation, or a concentration gradient. In this regard, phases may be characterized according to one or more chemical and/or physical properties having regard to one or more components in order to delineate between phases/regions of a functional product and/or a functional precursor product. A combination of one or more phases/regions may be considered a single concentration gradient. In the context of an intermediate or final product structure, there may be one or more phases.

The term “resin” is understood to be a solid or viscous material which provides a polymer after polymerization via, for example, curing.

The term “concentration gradient” is understood to be spatial positioning of one or more molecules/ions from a region having a higher concentration of the one or more molecules/ions to a region having a lower concentration of the one or more molecules/ions.

The term “orthogonal polymerization” is understood to include the ability to perform multiple polymerization reactions independently (orthogonally), for example, in a single reaction vessel. For example, a mechanism of a polymerization reaction of at least one first polymerizable component is different than a mechanism of the polymerization reaction of at least one second polymerizable component. In another example, a sequence of chemical reaction(s) of converting at least one first polymerizable component that has at least one first monomer and/or at least one first cross-linking agent to at least one first polymer differs from a sequence of chemical reaction(s) of converting at least one second polymerizable component that has at least one second monomer and/or at least one second cross-linking agent to at least one second polymer. The chemical reaction(s) include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/crosslinking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/crosslinking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).

The term “thermodynamic miscibility” is understood to be governed by the Gibbs free energy of mixing. For example, as a first polymer forms from a first monomer and/or a first cross-linking agent, the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of a second monomer and/or a second cross-linking agent in the polymer/monomer mixture. In other examples, the degree of phase separation can depend on the solubility and balance of intermolecular forces between each component (each set of monomer(s)/crosslinker(s)). Incompatible functional groups such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.

The term “modulus of elasticity” of a polymer is understood to be a number that measures an object or substance's resistance to being deformed elastically (i.e., non-permanently) when a force is applied to it.

The term “tensile strength” of a polymer is understood to be a measure of the ability of a polymer to withstand a longitudinal stress before permanent deformation occurs.

The term “functional product” is considered herein to be a product that performs at least one function. It may encompass a product that has, for example, one or more chemical, mechanical (including structural), magnetic, thermal, electrical, optical, electrochemical, protective, and catalytic properties. It could also, or instead, include a product that has an aesthetically pleasing property. Functional products can include a functional material such as a functionally graded material (FGM), and more specifically, a functionally graded composite material (FGCM). FGMs may be applied in a variety of industries, including, for example, aerospace, automobile, biomedical, defence, electrical/electronic, energy, marine, mining, opto-electronics, thermoelectronics, dentistry, and sports. FGMs may be used under a variety of conditions, including extreme temperature and wear conditions.

The term “interface”, “functional interface” or “functional precursor interface” refers to a region or surface of a functional and/or functional precursor product, which can include a surface of an intermediate structure in or comes into contact with another region/phase/material. For example, the interface may be a functional and/or functional precursor coating on the product (eg at an exterior surface) or as a layer/region within the product. The product may be an intermediate structure, which is further processed (e.g. further layered/coated) such that the exterior surface now acts as an interface between the intermediate structure and the additional layer/coating. In another example, the interface may be a graded functional and/or functional precursor material, the interface may be the region of the product where there is a certain concentration range of functional and/or functional precursor components to provide a function of the product. In a further example, the interface may be a functional and/or functional precursor composite material, the interface may be the region of the product where the composite provides a function of the product.

The term “particle” refers to a particle with any suitable size. In embodiments, the particle has an average particle size of about 10 nm to about 150 μm in diameter, for example, ranging from about 10 nm to about 100 μm; about 25 nm to about 100 μm; about 10 nm to about 50 μm; about 25 nm to about 50 μm; about 10 nm to about 25 μm; about 25 nm to about 25 μm; about 10 nm to about 10 μm; about 25 nm to about 10 μm; about 10 nm to about 5 μm; about 25 nm to about 5 μm; about 10 nm to about 2.5 μm; about 25 nm to about 2.5 μm; about 10 nm to about 500 nm; about 25 nm to about 500 nm; about 10 nm to about 250 nm; about 25 nm to about 250 nm; about 10 nm to about 100 nm; about 25 nm to about 100 nm; or about 50 nm to about 100 nm. The term “particle” as used herein thus includes “nanoparticle,” which is considered herein to be a particle having a diameter less than about 1000 nm, and “microparticle,” considered herein to be a particle having a diameter ranging from about 1 μm to about 1000 μm. In some embodiments, the particles described herein can be any shape, including generally spherical.

The term “coating” refers to a substantially homogenous layer (2D or 3D) or region within or on a product.

The term “functional coating” or “functional precursor coating” refers to a substantially homogenous layer (2D or 3D) or region of one or more functional and/or functional precursor components within or on a functional and/or functional precursor product. For example, the coating is a substantially homogenous layer (2D or 3D) of one or more functional and/or functional precursor components at or is an interface of the product. In another example, the coating of functional and/or functional precursor component(s) may be layered on a polymer (e.g. matrix or scaffold) but the coating (e.g. nanoparticles or a distinct polymer coating of functional and/or functional precursor components) itself is not per se distributed within (e.g. incorporated in) the polymer.

The term “graded” refers to the presence of a concentration gradient of one or more components. For example, a concentration gradient of one or more functional and/or functional precursor components, where the highest concentration of one or more of the functional and/or functional precursor components is at an interface of a product. In embodiments, the components of a concentration gradient are distributed within a polymer (e.g. matrix or scaffold) of the product and such non-homogenous graded functional and/or functional precursor material may exhibit changes in microstructures and/or composition through different regions of the product. The concentration gradient of a given component may change uniformly or change from shallow to steeper gradients (and vice-versa) through different regions of a product.

The term “composite” refers to a material made from two or more different components having different physical and/or chemical properties that, when combined, produce a material with characteristics different from the individual components themselves. The individual components remain as individual components within the product. For example, the functional and/or functional precursor products may have regions (e.g. functional and/or functional precursor interface) or phases of one or more functional and/or functional precursor components that are not phase separated from a polymer (e.g. matrix or scaffold), and that are not distributed in a polymer as a concentration gradient. In another example, the functional and/or functional precursor products may have regions (e.g. functional and/or functional precursor interface) or phases of one or more functional and/or functional precursor components at a functional interface that are not phase separated from a polymer (e.g. matrix or scaffold), and that are not distributed in a polymer as a concentration gradient. In certain embodiments, composite concentrations and distributions of functional and/or functional precursor components are substantially the same as the starting composition of components prior to polymerization of a polymerizable component (e.g. resin) to form the polymer (e.g. matrix or scaffold) of the product.

The term “functional group” refers to a specific group of atoms that has its own characteristic properties, regardless of the other atoms present in a compound. Common examples are alkenes, alkynes, alcohols, amines, amides, carboxylic acids, ketones, esters, epoxides, and ethers.

It is further to be understood that all amounts are approximate and are provided for description. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, suitable methods and materials are described below.

Methods

In general, the method is directed to making a polymeric product. The polymeric product can be a functional product, a functional precursor product, or a combination of a functional and functional precursor product. The method described herein may be used in vat polymerization 3D printing. Examples of vat polymerization 3D printing are stereolithography and digital light processing (FIG. 23 ).

In an embodiment, the method for making a product comprises a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product. The method may further comprise c) polymerizing the at least one second polymerizable component to form at least one second polymer. In embodiments, the method described herein is capable of controlling the placement/positioning of components(s) and/or polymer(s) (e.g. spatial positioning, spatially controlled positioning, etc.). For example, the method may provide selective positioning of component(s) and/or polymer(s) in a product (e.g. 2D or 3D structure). Therefore, the product may be designed such that specifically selected region(s) have one type of functionality and other region(s) have other type(s) of functionality. Such a method can provide spatially controlled functionality in the product. In such examples, the selected region(s) and unselected region(s) are near, adjacent, and/or coupled to each other. For instance, the first polymer(s) in the selected region(s) and the second polymer(s) in the unselected region(s) are near, adjacent, and/or coupled to each other.

In other embodiments, the method described herein includes orthogonal polymerization, different rates of polymerization, and/or thermodynamic miscibility.

For example, with respect to orthogonal polymerization, each of the polymerization reactions proceed via different mechanisms. In a specific embodiment, a mechanism of a polymerization reaction of the at least one first polymerizable component is different from a mechanism of a polymerization reaction of the at least one second polymerizable component. Other embodiments may include as follows: a sequence of chemical reaction(s) of converting the at least one first polymerizable component (e.g. at least one first monomer and/or at least one first cross-linking agent) to the at least one first polymer, which differs from a sequence of chemical reaction(s) of converting the at least one second polymerizable component (e.g. at least one second monomer and/or at least one second cross-linking agent) to the at least one second polymer. The chemical reaction(s) may include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).

With respect to the different rates of polymerization, each of the polymerization reactions may proceed via different rates. For example, the rate of polymerizing the at least one first polymerizable component to form at least one first polymer is faster or slower than the rate of polymerizing the at least one second polymerizable component to form at least one second polymer. With respect to the rates of polymerization and in view of the different mechanisms of polymerization, certain monomer(s) that undergo radical polymerization may form polymers at a faster rate than other monomer(s) that undergo cationic polymerization. For example, (meth)acrylate-based monomers via radical polymerization may form polymers at a faster rate than epoxides via cationic polymerization. Different polymerization rates can also occur within the same mechanism of polymerization (e.g. radical polymerization). For example, acrylates tend to be more reactive in a radical polymerization reaction compared to a radical polymerization reaction with (meth)acrylates. In other embodiments, polymerization rates can increase with increasing monomer functionality, for example, from mono- to di- to tri-functional groups. In certain embodiments, the order of polymerization rates from fastest to slowest is tri-functionalized acrylates>di-functionalized acrylates>mono-functionalized acrylates>(meth)acrylates>epoxides. The at least one first and the at least one second polymerizable components may be selected from monomer(s)/crosslinker(s) of these categories.

With respect to the thermodynamic miscibility, each of the polymerization reactions may affect the thermodynamic miscibility. For example, thermodynamic miscibility of the at least one first polymer is different from thermodynamic miscibility of the at least one second polymer. In another example, with respect to a combination of the at least one first polymerizable component and the at least one second polymerizable component, as the at least one first polymerizable component (e.g. a first monomer and/or a first cross-linking agent) polymerizes to form the at least one first polymer, the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of the at least one second polymerizable component (e.g. a second monomer and/or a second cross-linking agent) in the polymer/monomer mixture, which causes phase separation. In other examples, the degree of phase separation can depend on the solubility and balance of intermolecular forces between each component (each of the first and second monomer(s)/cross-linking agent(s)). Incompatible functional groups in the polymerizable components can affect thermodynamic miscibility, such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.

These different mechanisms, rates of polymerization, and miscibilities are properties that can control the placement/positioning of component(s) and/or polymer(s) within a product.

With respect to a) in the method, the composition has at least one first polymerizable component and at least one second polymerizable component. In an embodiment, the composition is a substantially homogeneous composition. In a further embodiment, the substantially homogeneous composition is a substantially homogeneous mixture.

Polymerization may be achieved via initiation of polymerization in selected region(s) of the composition (e.g. mixture) having at least one polymerizable component and at least one second polymerizable component, whereby such polymerization can induce phase separation. In embodiments, polymerization occurs in the selected region(s) to form a first polymer(s) and the unselected region(s) has the second polymerizable component(s). There may be some first polymerizable component(s) in the unselected region(s) or some second polymerizable component(s) in the selected region(s). The at least one polymerizable component and at least one second polymerizable component may be contained in, for example, as reservoir prior to polymerization of the selected region(s).

In embodiments, the polymerizing in b) and/or c) may comprise photopolymerization (e.g. photoinduced polymerization). In another embodiment, the at least one first polymerizable component has at least one first monomer and/or at least one first cross-linking agent. In another embodiment, the at least one second polymerizable component has at least one second monomer and/or at least one second cross-linking agent. In embodiments, the composition further comprises at least one photoinitiator. Polymerization may also occur via free-radical polymerization without a photoinitiator.

With respect to the polymerizing in b), the polymerizing may be achieved by exposing the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) to a radiation and/or a heat source (e.g. light or heat) capable of initiating polymerization of the at least one first polymerizable component. The radiation and/or heat source may be selected from a UV-Vis source, a laser, an electron beam, a gamma-radiation, an IR (heat) source, LED, microwave radiation, plasma and thermal treatment. With respect to the polymerizing in c), the polymerizing may be achieved by exposing the at least one first polymer and the at least one second polymerizable component to a radiation and/or a heat source capable of initiating polymerization of the at least one second polymerizable component. The radiation and/or heat source may be selected from a UV-Vis source, a laser, an electron beam, a gamma-radiation, an IR (heat) source, LED, microwave radiation, plasma and thermal treatment. Therefore, polymerization is generally photopolymerization and/or thermal polymerization.

In embodiments, to achieve selective positioning of component(s) and/or polymer(s) to provide spatially controlled functionality in a product, polymerization of selected regions of the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) is done using light and/or heat. For example, the polymerizable component(s) are selectively irradiated at a certain wavelength such that one type of polymerizable component polymerizes as opposed to another type. For instance, irradiating the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) with a light comprising at least one wavelength in a range of from about 250 to about 800 nm, so as to polymerize the irradiated portion of the mixture, thereby providing polymerized and unpolymerized regions to form an intermediate structure. In embodiments, the intermediate structure is designed to have region(s) without the polymer (e.g. spaces, holes, apertures, depressions, pores, etc.) or having less polymer. In another example, the intermediate structure is designed such that the patterned light and pre-selected structure causes the second polymerizable component(s) that have a slower polymerization rate, orthogonal reactivity, and/or lower solubility to diffuse towards unilluminated regions and to be spatially confined to “spaces” or certain regions within or between the intermediate product's structure, formed from the polymerization of the first polymerizable component. For example, layers of hexagons (FIG. 27 a)) with support bridges 3D printed with the first polymerizable component are spaced such that the second polymerizable component and/or first component(s) (e.g. functional material) phase separates and diffuses to the unilluminated spaces/regions in the intermediate structure and is then confined to the region/space after forming the polymer from the second polymerizable component via UV or thermal initiation. This is in contrast to a structure, such as a solid rectangular prism that is not printed/illuminated to have spaces or regions where the second polymerizable or functional material component can be confined as it is formed and phase separates. Another example includes the diffusion of the second polymerizable component to be confined within closed regions of the 3D printed structure (e.g. closed filled cubes). The phase separation and architecture of the final 3D printed structure is defined by the kinetics and/or mechanisms of polymerization and/or thermodynamic miscibility of the components and the patterned illumination. In another example, a second stage UV or thermal cure is used to polymerize the second polymerizable component that is formed by an orthogonal polymerization mechanism, for example, not photopolymerized by the 405 nm laser of the 3D printer. The second stage UV or thermal cure polymerizes the second polymerizable component in regions that were not illuminated by the patterned light, but contain the second polymerizable component due to an additional infiltration step or due to phase separation during 3D printing. In another examples, the irradiated portion may be patterned through, for example, by a direct writing application of light, or by interference, nanoimprint, or diffraction gradient lithography, or by stereolithography, holography, or digital light projection (DLP). Patterned light is understood to include micro-patterned light. When patterned irradiation is used, a variable pattern and/or a pattern that is held constant over time may be used (e.g. fixed pattern). If variable, each irradiating step may be any suitable time or duration depending on factors such as the intensity of the irradiation, the rate of polymerization, etc In embodiments, the method provides selective positioning/placement of component(s) and/or polymer(s) in a product (e.g. 2D or 3D product).

The polymerization may be achieved via 3D printing and more particularly by vat polymerization 3D printing methods. In an embodiment, the 3D printing uses photoactivation and may be selected from stereolithographic (SLA) printing, digital light processing (DLP), and volumetric printing. In an embodiment, the polymerizing in b) is photopolymerization and the polymerizing in c) is photopolymerization and/or thermal polymerization. For example, the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) is irradiated with patterned light, whereby the at least one first polymerizable component polymerizes to form the 3D printed structure having the at least one first polymer and a separate phase of at least one second polymerizable monomer, which diffused away from region of the at least one first polymer. The irradiation of the composition can define the 3D printed structure. In embodiments, shorter irradiation time (e.g. shorter laser time) can result in a smaller amount of crosslinking/polymerization and lead to a polymer with different properties (i.e. more flexible) than a polymer that is more crosslinked/polymerized with longer laser exposure time. By applying a UV or thermal cure step of a desired time/temperature, the crosslinking density, amount of polymerization, and desired properties the first and or second polymerization can be achieved. Shorter wavelength may refer to a light source with a lower wavelength, such as in the 300 nm range as opposed to the 405 nm laser of a 3D printer. Using a second polymerizable component that polymerizes with lower wavelength UV light, the monomers of the second polymerizable component phase separate into spaces and are confined in such spaces. A second stage UV cure (lower wavelength than the 405 nm laser) is used after the 3D part is printed in order to completely polymerize the second polymerizable component and form the two polymers (e.g. solid phases). The 3D printed structure may be irradiated or heated with patterned light or heat to polymerize the at least one second polymerizable component (in the areas or volumes of the 3D printed structure, having a majority of the second polymerizable component) to the at least one second polymer to form the 3D printed product. In an example of the 3D printed product, the resultant design used to irradiate or heat the 3D printed structure with patterned light or heat provided a continuity (e.g. the phases are near/adjacent to one another) in the 3D printed product. A specific example is shown in FIG. 24 . In FIG. 24 , (1) shows a substantially homogeneous resin mixture prior to photopolymerization, (2) shows the first polymerizable component (black) separate from the second polymerizable component (grey), (3) shows selective photopolymerization of the mixture with patterned light to polymerize the first polymerizable component to form a first polymer (black) without polymerizing the second polymerizable component (grey), (4) shows that the second polymerizable component (grey) has subsequently been polymerized to form a second polymer, and (5) shows a brick-and-mortar type structure of a 3D printed product. In this example, there is a higher concentration of the first polymerizable component compared to the second polymerizable component and the first polymerizable component polymerizes at a faster rate than the second polymerizable component based on the selected patterned light. An example of the method shown in FIG. 24 is a holographic PIPS. The methods described herein can be used to build a bio-inspired pattern of materials at the micron-scale. In other examples, when the composition is initiated using a 405 nm laser, the first polymerizable component(s) has a faster polymerization rate compared to the second polymerizable component(s). In another example, when the composition is initiated using a 405 nm laser and after the first polymerizable component(s) polymerizes to form a 3D printed structure, the second polymerizable component(s) is only polymerized with a lower wavelength UV light cure (second stage UV cure).

Selective photopolymerization of the at least one first polymerizable component to form the at least one first polymer, which can result in the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)) phase separating and/or diffusing away from the first polymer, which is referred to as polymerization induced phase separation, PIPS, FIG. 24 . Without being bound by theory, it is believed that due to the kinetics and thermodynamics of the unreacted second polymerizable component(s) in proximity to the polymerizing mixture and may be driven by the minimization of the overall free energy.

In other embodiments, the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) of the at least one first polymerizable component and the at least one second polymerizable component is irradiated with patterned light to cause the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)), that has a slower polymerization rate, orthogonal reactivity, and/or lower solubility, to diffuse towards unilluminated regions of the 3D printed structure of the at least one first polymer, and to be spatially confined to “spaces” or certain regions (e.g. varying shapes) within or between the 3D printed structure of the faster polymerizing first polymerizable component (e.g. first monomer(s) and/or first cross-linking agent(s)). In another embodiment, the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) of the at least one first polymerizable component and the at least one second polymerizable component is irradiated with patterned light to cause the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)), that has a slower polymerization rate, orthogonal reactivity, and/or lower solubility, to diffuse towards unilluminated regions of the 3D printed structure of the at least one first polymer, and to be confined within “spaces” or certain regions (e.g. closed filled cubes) within the 3D printed structure of the faster polymerizing first polymerizable component (e.g. first monomer(s) and/or first cross-linking agent(s)). The 3D printed structure is irradiated or heated (e.g. thermal or UV curing) such that the at least one second polymerizable component forms the at least one second polymer. See for example, FIG. 25 showing spatially controlled position of polymers. In FIG. 25 , (1) shows a design print file for a 3D product with microscale patterns consisting of illuminated (black) and masked (white) areas (image excludes support structures that may be needed in between the layers), (2) shows vat polymerization of substantially homogeneous resin mixture using micro-patterned light motif, wherein the mixture has a first polymerizable component and a second polymerizable component, and (3) shows the 3D printed product with the first polymer (black) and the second polymer (grey).

In another embodiment, the method comprises combining a first polymerizable component(s) and a second polymerizable component(s). The first polymerizable component(s) comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties. The second polymerizable component(s) comprises thermal curable monomer(s) and/or crosslinking agent(s) in suitable amounts to provide the desired optimal properties. The ratio of first polymerizable and second polymerizable component(s) was varied to optimize the phase separation and physical properties. The first polymerizable component(s) and second polymerizable component(s) were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component(s), forming a 3D-printed polymer product having spaces or closed regions that confine, mostly, the second polymerizable component(s). The second polymerizable component(s) are polymerized via thermal or UV curing. In this embodiment, phase separation occurs due to orthogonal polymerization mechanisms and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s). In one example, the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component and the second polymerizable component. For example, the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that are substantially free of the “hard” polymer (e.g. spaces) but including the “soft” polymer resin. The “hard” polymer product was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having closed regions that are substantially free of the “hard” polymer (e.g. spaces) but confine the “soft” polymer resin (e.g. resin filled closed regions). The “hard” polymer product having the confined “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the method comprises combining a first polymerizable component(s) and a second polymerizable component(s). The first polymerizable component(s) comprise monomer(s) and/or cross-linking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties. The second polymerizable component(s) comprises monomer(s) and/or crosslinker(s), and photoinitiator(s) in suitable amounts to provide the desired optimal properties. The ratio of the first polymerizable and second polymerizable components was varied to optimize the phase separation and physical properties. The first polymerizable component(s) and second polymerizable component(s) were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component polymer resin, forming a 3D-printed polymer product having closed regions that confine, mostly, the second polymerizable component(s). The second polymerizable component are polymerized via thermal or UV curing. In this embodiment, phase separation occurs due to orthogonal polymerization mechanisms, different rates of polymerization, and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s). In one example, the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component(s) and the second polymerizable component(s).

In another embodiment, the method comprises combining a “soft” polymer resin and a “hard” polymerizable resin. The “soft” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The “hard” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The ratio of “soft” to “hard” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “soft” and “hard” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “soft” polymer resin, forming a “soft” polymer product (e.g. 3D-printed polymer product) having closed regions that confine mostly “hard” polymer resin and some “soft” polymer resin (e.g. resin filled closed regions). The “soft” polymer product having the confined “hard” polymer resin and some “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), one or both of which contains an epoxide functional group, and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin (e.g. UV curable) or amine(s) resin (thermal curable) and a cationic initiator in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that include the “soft” polymer resin (e.g. filled regions). The “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to cause the pendent epoxide functional group of the 3D printed “hard” polymer to polymerize with the “soft” resin. The final product comprises both “soft” and “hard” polymers.

Therefore, in embodiments, the method for making a product comprises a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and c) polymerizing the at least one second polymerizable component to form at least one second polymer, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product. The first polymer(s) may have at least one functional group that, in c), reacts with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s). For example, the first polymer(s) are bonded/tethered to the second polymer(s) and/or the second polymerizable component(s).

In another embodiment, the method comprises combining a “hard” polymer resin, a “soft” polymerizable resin and a photoinitiator. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), with slower kinetics and/or incompatible functional groups, in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product. Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs. non-polar, aromatic vs. aliphatic, or aliphatic vs. polydimethylsiloxane-functionalized). The “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin. The final product comprises both “soft” and “hard” polymers.

In another embodiment, the method comprises combining a “hard” polymer resin, a “soft” polymerizable resin, a photoinitiator, a cationic photoinitiator, and a photosensitizer. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide monomer(s) and epoxide crosslinking agent(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product. Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs. non-polar, aromatic vs. aliphatic, or aliphatic vs. polydimethylsiloxane-functionalized). The “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin. The final product comprises both “soft” and “hard” polymers.

In embodiments, the phase separation and architecture of the final 3D printed product may be defined by the kinetics, mechanisms of polymerization, and/or thermodynamic miscibility of the components and the patterned illumination of the 3D structure. The resulting unique structural motifs can create an overall product with different or improved physical/chemical properties. For example, alternating “hard” and “soft” phases (e.g. “hard” and “soft” polymers) improves the overall mechanical properties compared to similar structures of only the individual polymer. Phase separated functional materials (e.g. first polymer(s) and second polymer(s)) allow certain regions to be conductive, responsive to external stimuli, etc.

Therefore, the first polymer(s) (e.g. formed from the first monomer(s) and/or the first cross-linking agent(s)) and the second polymer(s) (e.g. formed from the second monomer(s) and/or the second cross-linking agent(s)) can have different physical/chemical properties. For example, the first polymer(s) formed from polymerizing the first polymerizable component(s) may have mechanical properties that are characterized as “hard” or “soft”, while the second polymer(s) formed from polymerizing the slower, orthogonal and/or lower soluble second polymerizable component(s) may have mechanical properties that are characterized to be the opposite of the first polymer(s); “soft” or “hard”. In embodiments, a “hard” polymer may have the following mechanical properties: about 2000 to about 4000 MPa range in modulus of elasticity, about 40 to about 65 MPa range in tensile strength, and/or about 10 to about 25% range in elongation at break; a “soft” polymer may have the following mechanical properties: about 0.5 to about 5.0 MPa range in tensile strength and/or about 45 to about 250% range in elongation at break.

In other examples, the first polymer(s) and the second polymer(s) may be nanomaterials, dyes/pigments, conductive, tolerant, piezoelectric, responsive to external stimuli, and/or different environmental conditions, etc. External stimuli or environmental conditions can include temperature, pressure, surrounding environment (water or other chemicals), magnetic field, etc.

In another embodiment of a method, the method for making a product comprises a) polymerizing at least one first polymerizable component to form at least one first polymer structure; b) combining the at least one first polymer structure and at least one first component, and wherein the at least one first component comprises at least one functional component, at least one functional precursor component, or combinations thereof. In another embodiment, the method further comprises c) polymerizing the at least one first component to form at least one second polymer, wherein the at least one first component comprises at least one second polymerizable component and wherein the product comprises the at least one second polymer and at least one first polymer structure. In embodiments, the first polymer structure is a structure including space(s)/region(s) containing the first component(s).

In a certain embodiment, the method comprises photopolymerization of the first polymerizable component to form a 3D printed intermediate structure while the first component(s) (e.g. polymer or second polymerizable component) is added in an additional step after 3D printing. If the first component(s) are the second polymerizable component, it may be polymerized using thermal polymerization, orthogonal polymerization mechanism, or by a second stage UV cure. The 3D structure formed from the first polymerizable component contains spaces/holes. The spaces in the 3D printed structure were filled by either submerging the structure in the first component(s) or by capillary action and then thermally or UV cured if the second polymerizable component(s). The spacing within the 3D structure and the amount of first component(s) varied to optimize the phase separation and resulting material properties. In one example, the final product comprises both “soft” and “hard” polymers with the “soft” polymer infiltrated into the “hard” 3D printed polymer. In another embodiment, the method comprises combining (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s) and a photoinitiator in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions (e.g. empty spaces) substantially free of the “hard” polymer resin. A “soft” polymer resin, having epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer, was made. The “hard” polymer product was combined (e.g. submerging, immersing, capillary action, etc.) with the “soft” polymer resin, whereby the “soft” polymer resin fills the spaces in the “hard” polymer product and then heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to to polymerize the “soft” resin. The final product comprises both “soft” and “hard” polymers.

In another embodiment, the method comprises combining the first polymerizable component to form the 3D printed structure and a first component(s) to phase separate, wherein the first component(s) is a polymer or derivative thereof. The first polymerizable component comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties. The first component(s) (e.g. linear polymer, small molecule, etc.) phase separates due to thermodynamic miscibility of the first polymerizable component and the at least one first component(s). The ratio of first polymerizable component(s) and first component(s) was varied to optimize the phase separation and desired resulting properties. The first polymerizable component(s) and first component(s) were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component, forming a 3D-printed polymer product in which the first component(s) is either confined within the structure and phase separated out of the spaces or phase separated out of the 3D structure and into the spaces.

In embodiments, the polymerizing in a), b) or c) may be performed for a time period sufficient for the polymerizable component(s) to substantially polymerize (e.g. solidify or reach a substantial gel-point), which will depend on the type of polymerizable component(s). One skilled in the art would be able to determine the time period. In typical embodiments, time periods are selected such that at least about 15% of the polymerizable component(s) convert to polymer(s), or at least about 30% of the polymerizable component(s) convert to polymer(s), or at least about 40% of the polymerizable component(s) convert to polymer(s), or at least about 50% of the polymerizable component(s) convert to polymer(s), or at least about 60% of the polymerizable component(s) convert to polymer(s), or about 40% to about 60% of the polymerizable component(s) convert to polymer(s). These percentages are based on the total weight of the at least one polymerizable component. In typical embodiments, there is sufficient polymerization for the polymerizable component(s) to generate, for example, a 3D-product.

With respect to the amount of the at least one polymerizable component(s) that may be used in embodiments, any suitable amount can be used. One embodiment includes from about 10% to about 99% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 20% to about 99% by weight, from about 30% to about 99% by weight, from about 40% to about 99% by weight, from about 50% to about 99% by weight, from about 60% to about 99% by weight, from about 70% to about 99% by weight, or from about 80% to about 99% by weight based on the weight of the homogeneous mixture.

The product may be any suitable structure/object. The product may be a 3D- or 2D-product. The product may have one or more phases. In embodiments, the product is a film or a 3D-product. The product may have any desired geometry (e.g. shape). Various 3D structures and functional high aspect ratio coatings and functional patterns in devices, such as sensors, optoelectronic devices, solar cells, electrodes, RFID tags, antennas, electroluminescent devices, power sources and connectors for circuit boards may be fabricated. The product may have at least one functional property selected from the group consisting of chemical properties, mechanical properties, magnetic properties, optical properties, insulating or protective properties (e.g. towards heat, radiation, mechanical abrasion), properties, electrical properties, electrochemical, catalytic properties, and combinations thereof. In other embodiments, the product is at least one of stretchable, flexible, lightweight, porous, conductive, non-conductive, surface durable, increased surface area, hydrophobic, biocompatible, anti-bacterial, mould resistant, wear-resistant, heat resistant, cold resistant, improved surface properties (antifouling), reduce flame retardancy, and combinations thereof. In typical embodiments, the surface of the functional product (e.g. coating itself, coating of 3D-product, etc.) imparts the product with the functionality. In embodiments, the product is multifunctional and/or is a precursor product that is a precursor to a multifunctional product. The product may be used for various applications, including metal/semiconductor, catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices. Other embodiments of commercial uses for the product include, for example, metamaterials with millimetre wave communication devices, objects embedded with self-healing materials, 3D objects with responsive materials (ferrofluidics, piezoelectric materials, conductive channels, etc.) for soft robotics, shape recovery objects with controlled placement/positioning of actuation material, encryption or anti-counterfeiting with treatment of spatially controlled structures with fluorescent ink, and/or parts for structural electronics (sensors and energy devices) with spatially controlled placement/positioning of conductive material within an object.

In embodiments, the product is conductive. The product may be selected to be any suitable conductivity. For example, it may have a conductivity (e.g. resistance) of at least about 1 Ω/cm; at least about 2 Ω/cm; at least about 5 Ω/cm; at least about 10 Ω/cm; at least about 15 Ω/cm; or at least about 20 Ω/cm. In other examples, the conductivity may be from about 1 to about 50 Ω/cm; from about 2 to about 50 Ω/cm; from about 5 to about 50 Ω/cm; from about 10 to about 50 Ω/cm; from about 15 to about 50 Ω/cm; from about 20 to about 50 Ω/cm; from about 1 to about 40 Ω/cm; from about 2 to about 40 Ω/cm; from about 5 to about 40 Ω/cm; from about 10 to about 40 Ω/cm; from about 15 to about 40 Ω/cm; from about 20 to about 40 Ω/cm; from about 1 to about 30 Ω/cm; from about 2 to about 30 Ω/cm; from about 5 to about 30 Ω/cm; from about 10 to about 30 Ω/cm; from about 15 to about 30 Ω/cm; from about 20 to about 30 Ω/cm; from about 1 to about 25 Ω/cm; from about 2 to about 25 Ω/cm; from about 5 to about 25 Ω/cm; from about 10 to about 25 Ω/cm; from about 15 to about 25 Ω/cm; from about 20 to about 25 Ω/cm; from about 10 to about 23 Ω/cm; or about 18 to about 23 Ω/cm.

In an embodiment, the method described herein can further comprise at least one first component. The first component(s) comprises at least one functional component, at least one functional precursor component, or a combination thereof. For example, the first component(s) can be added to the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). In another embodiment, the method comprises converting the at least one functional precursor component into at least one second functional component. In an embodiment, the at least one second functional component is different from said at least one functional component. In another embodiment, the at least one second functional component is the same as the at least one functional component. The converting may comprise sintering and/or pyrolyzing, for example, as described above. In some embodiments, the at least one functional precursor component is capable of being converted into at least one second functional component via sintering. The sintering may be at least one of thermal sintering, UV-VIS radiation sintering, and laser sintering. In embodiments, sintering may occur during or after printing. In some embodiments, the method may thus comprise an additional step of converting a metal precursor into a metal form which may thereafter be sintered.

In embodiments, the method further comprises sintering the product formed from b) or c), pyrolyzing the product formed from b) or c), or sintering and pyrolyzing the product formed from b) or c). In more specific embodiments, sintering is thermal sintering, UV-VIS radiation sintering, laser sintering or any combination thereof. In typical embodiments, minimum thermal sintering temperatures are selected based on a minimum temperature for converting the functional precursor to the functional product. Maximum thermal sintering temperatures may be selected based on a maximum temperature that the functional precursor and/or the functional product may be heated to without causing substantive decomposition or degradation. With respect to thermal sintering, the temperature ranges include, but are not limited thereto, from about 50° C. to about 300° C., or about 50° C. to about 280° C., or about 100° C. to about 280° C., or about 100° C. to about 270° C., or about 150° C. to about 280° C., or about 160° C. to about 270° C., or about 180° C. to about 250° C., or about 230° C. to about 250° C. Thermal sintering may occur under air or under inert condition(s), such as nitrogen. Thermal sintering may be performed for a time in ranges of about 15 minutes to about 180 minutes, or about 30 minutes to about 120 minutes, or about 45 minutes to about 60 minutes. In typical embodiments, sintering occurs under nitrogen with about 500 ppm oxygen. With respect to UV-VIS radiation sintering, sintering energies may range from about 1 J/cm² to about 30 J/cm², or about 2 J/cm² to about 10 J/cm², or about 2.5 J/cm² to about 5 J/cm², or about 2.4 J/cm² to about 3.1 J/cm². In certain embodiments, the pulse widths are about 500 s to about 5000 s, or about 1000 s to about 4000 s, or about 2500 s to about 3000 s. In typical embodiments, UV-VIS radiation sintering occurs under air. With respect to pyrolyzing, the temperature ranges include, but are not limited thereto, from about 350° C. to about 1200° C., or about 400° C. to about 900° C., or about 600° C. to about 800° C., or about 700° C. to about 800° C. Pyrolyzing may be performed for a time in a range of about 1 to about 60 minutes. Pyrolyzing may occur under air or under inert condition(s), such as nitrogen.

In embodiments, the first and second polymer(s) have a weight average molecular weight of about 10,000 to about 10,000,000, or about 10,000 to about 5,000 000, or about 10,000 to about 1,000,000, or about 50,000 to about 1,000,000, or about 50,000 to about 500,000. It is understood that the weight average molecular weight may approach infinity and includes cross-linked polymeric network(s).

With respect to the at least one first and second polymerizable component(s), each, independently, may comprise at least one monomer and/or at least one oligomer. The at least one first and second polymerizable component(s) may comprise at least one liquid monomer and/or at least one liquid oligomer. In a certain embodiment, the at least one first polymerizable component and/or the at least one second polymerizable component comprises at least one resin. Some examples include resins based on epoxies, vinyl ethers, acrylates, urethane-acrylates, methacrylates, acrylamides, thiol-ene based resins, styrene, siloxanes, silicones, and any functionalized derivatives thereof (e.g. fluorinated methacrylates, PEG-functionalized methacrylates or epoxies). The at least one resin may comprise at least one commercial resin. In particular, typical examples of the at least one resin comprises at least one commercial resin for 3D printing such as, and without being limited thereto, 3D printing via photoactivation (e.g. stereolithographic (SLA) printing or digital light processing (DLP)). In further embodiments, the at least one resin may comprise at least one acrylate based-resin. The monomer resins may be elastomers or pre-ceramic polymers.

In embodiments, the monomers and oligomers are selected according to their physico-chemical and chemical properties, such as monomer viscosity and/or surface tension, and/or polymer elasticity and/or hardness, number of polymerizable groups, and according to the printing method and the polymerization reaction type, e.g., the radiation source or heat source of choice. With respect to elasticity or hardness, some embodiments include modulus value ranges of from about 0.1 MPa to about 8000 MPa. In some embodiments, the monomers are selected from acid containing monomers, acrylic monomers, amine containing monomers, cross-linking acrylic monomers, dual reactive acrylic monomers, epoxides/anhydrides/imides, fluorescent acrylic monomers, fluorinated acrylic monomers, high or low refractive index monomers, hydroxy containing monomers, mono and difunctional glycol oligomeric monomers, styrenic monomers, vinyl and ethenyl monomers. In some embodiments, the monomers can polymerize to yield conductive polymers such as polypyrole and polyaniline. In some embodiments, the at least one monomer is selected from dipentaerythnitol hexaacrylate (DPHA) and trimethylolpropane triacrylate (TMPTA). In some embodiments, the at least one oligomer is selected from the group consisting of acrylates and vinyl containing molecules.

In other embodiments, the monomer can be any monomeric compound having a functional group, such as an activatable photopolymerizable group (photoinduced polymerization) that can propagate, for example, carbon-carbon, carbon-oxygen, carbon-nitrogen, or carbon-sulfur bond formation. In certain embodiments, the monomer is selected from mono-functional monomers (e.g. monomers with one functional group). During polymerization, the radical of the monofunctional monomer is formed and it will react with other monomers present to form oligomers and polymers. The resultant oligomers and polymers can have different properties depending on its structure. Some monomers may be selected depending on their flexibility, viscosity, curing rate, reactivity or toxicity. In one embodiment, the monomer is polymerized to form a polyacrylate such as polymethylmethacrylate, an unsaturated polyester, a saturated polyester, a polyolefin (polyethylenes, polypropylenes, polybutylenes, and the like), an alkyl resin, an epoxy polymer, a polyamide, a polyimide, a polyetherimide, a polyamideimide, a polyesterimide, a polyesteramideimide, polyurethanes, polycarbonates, polystyrenes, polyphenols, polyvinylesters, polysilicones, polyacetals, cellulose acetates, polyvinylchlorides, polyvinylacetates, polyvinyl alcohols polysulfones, polyphenylsulfones, polyethersulfones, polyketones, polyetherketones, poyletheretherketones, polybenzimidazoles, polybenzoxazoles, polybenzthiazoles, polyfluorocarbones, polyphenylene ethers, polyarylates, cyanate ester polymers, polystyrenes, polyacrylamide, polyvinylethers, copolymers of two or more thereof, and the like. In other embodiments, polyacrylates include polyisobornylacrylate, polyisobornylmethacrylate, polyethoxyethoxyethyl acrylate, poly-2-carboxyethylacrylate, polyethylhexylacrylate, poly-2-hydroxyethylacrylate, poly-2-phenoxylethylacrylate, poly-2-phenoxyethylmethacrylate, poly-2-ethylbutylmethacrylate, poly-9-anthracenylmethylmethacrylate, poly-4-chlorophenylacrylate, polycyclohexylacrylate, polydicyclopentenyloxyethyl acrylate, poly-2-(N,N-diethylamino)ethyl methacrylate, poly-dimethylaminoeopentyl acrylate, poly-caprolactone 2-(methacryloxy)ethylester, and polyfurfurylmethacrylate, poly(ethylene glycol)methacrylate, polyacrylic acid and poly(propylene glycol)methacrylate.

Monomers and oligomers that may be used, for example, include acrylic monomers such as monoacrylics, diacrylics, triacrylics, tetraacrylics, pentacrylics, etc. Examples of other monomers include ethyleneglycol methyl ether acrylate, N,N-diisobutyl-acrylamide, N-vinyl-pyrrolidone, (meth)acryloyl morpholine, 7-amino-3,7-dimethyloctyl, (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth)acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N,N-dimethyl (meth) acrylamide tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl(meth)acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono-(meth)acrylate, methyl triethylene diglycol (meth)acrylate, alkoxylated alkyl phenol acrylate, (poly)caprolactone acrylate ester from methylol-tetrahydrofuran, (poly)caprolactone acrylate ester from alkylol-dioxane, ethylene glycol phenyl ether acrylate, and methacryloxypropyl terminated polydimethylsiloxane.

Other monomers that may be used, for example, include epoxide monomers such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, allyl glycidyl ether, bis[4-(glycidyloxy)phenyl]methane, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclohexene oxide, dicyclopentadiene dioxide, 1,2,7,8-diepoxycyclooctane, 1,2,5,6-diepoxyoctane, styrene oxide, neopentyl glycol dilycidyl ether, glycidyl isopropyl ether, glycidyl 4-methoxyphenyl ether, 2-ethylhexyl glycidyl ether, (2,3-epoxypropyl)benzene, 1,2-epoxy-3-phenoxypropane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxyhexane, 1,27,8-diepoxyoctane, dilycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, and/or epoxycyclohexylethyl terminated polydimethylsiloxane.

With respect to the amount of the first and second monomer(s) that may be used in embodiments, any suitable amount can be used depending on the desired functional and/or functional precursor product. One embodiment includes from about 10% to about 99% by weight of the at least one monomer based on the weight of the composition. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.

With respect to the amount of the at least one monomer that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes from about 1% to about 90% by weight of the at least one monomer. In some embodiments, the amount is from about 1% to about 85% by weight, from about 1% to about 80% by weight, from about 1% to about 75% by weight, from about 5% to about 90% by weight, from about 10% to about 90% by weight, from about 15% to about 90% by weight, from about 20% to about 90% by weight, from about 25% to about 90% by weight, from about 35% to about 90% by weight, from about 40% to about 90% by weight, from about 45% to about 90% by weight, from about 5% to about 80% by weight, from about 10% to about 80% by weight, from about 15% to about 80% by weight, from about 20% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component.

With respect to the at least one cross-linking agent, it may be included in the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). Cross-linking agents may have one or more functional groups and, typically, have two or more functional groups (e.g. di-, tri-, tetra-, etc. functional cross-linking agents). In certain embodiments, the functional groups may be present at both ends of the cross-linking agent, forming branched polymerization, whereby the cross-linking agent may react with two or more polymers. In certain embodiments, a 2D product is formed with a monofunctional cross-linking agent and a 3D product is formed with a multifunctional cross-linking agent.

In embodiments, the morphology of a functional and/or functional precursor product (e.g. 3D printed product) may depend on the concentration (e.g. amount) of cross-linking agent. The concentration of the cross-linking agent may control the rate at which a polymer network forms. In one embodiment, when the cross-linking agent concentration is high, the rate at which the monomers form polymer networks (e.g. branched polymerization) are high. High rates of polymer network formation may limit the diffusion of slower reacting or non-polymerizing components and provide more uniform compositions such as composites in certain regions (e.g. portions) of the product. Conversely, in other embodiments, when cross-linking agent concentrations are low and the rates of polymer network formations are low, slower polymerizing monomers or non-polymerizing components (e.g. silver salt, nanoparticles, etc.) can diffuse towards regions where their solubilities are higher. Their solubilities may be higher towards the surface of the printed product, where the polymer concentration is low and the monomer concentration is high. Therefore, formulations with low cross-linking agent concentrations may lead to printed products (e.g. objects) where the slower polymerizing monomer or non-polymerizing component forms a coating in certain regions of the product. In other embodiments, intermediate cross-linking agent concentrations can generate graded compositions in certain regions of the product. In embodiments, therefore, the morphology of the functional and/or functional precursor product can be a function of cross-linking agent concentrations in compositions (e.g. substantially homogeneous compositions or substantially homogeneous mixtures) containing non-polymerizing functional and/or functional precursor components.

In embodiments, the amount of functional and/or functional precursor component at the surface of the functional and/or functional precursor product decreases with increased concentration of cross-linking agent. The concentration of functional and/or functional precursor component at the surface can determine the resistance value of the printed product. As the concentration of cross-linking agent increases, the resistance of the functional and/or functional precursor component at the surface (e.g. coating) increases in view of the lower concentration of the functional and/or functional precursor component at the surface.

With respect to the amount of the at least one cross-linking agent that may be used in embodiments, any suitable amount can be used depending on the desired functional and/or functional precursor product. For example, the amount of the at least one cross-linking agent can be used to tune the morphology of the functional and/or functional precursor product. One embodiment includes from about 10% to about 99% mol based on the composition. In some embodiments, the amount is from about 80% to about 99% mol, from about 85% to about 99% mol, from about 90% to about 99% mol, from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 35% to about 55% mol, from about 35% to about 50% mol, from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the composition.

With respect to the amount of the at least one cross-linking agent, based on the weight of the composition, that may be used in embodiments, any suitable amount can be used. One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.

With respect to the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes from about 10% to about 99% by weight of the at least one cross-linking agent. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).

In embodiments, the cross-linking agent is a radical reactive cross-linking agent. Examples of the radical reactive cross-linking agent include a methacrylic compound, an acrylic compound, a vinyl compound, and an allyl compound. Examples of suitable cross-linking agents which can be used to form polyacrylates include 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, bis(2-methacryloxyethyl)N,N-1,9-nonylene biscarbamate, 1,4-cyclohexanedimethanol dimethacrylate, and diacrylic urethane oligomers (reaction products of isocyanate terminate polyol and 2-hydroethylacrylate). Examples of triacrylates which can be used to form polyacrylates include tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. Examples of tetracrylates include pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, and ethoxylated pentaerythritol tetraacrylate. Examples of pentaacrylates include dipentaerythritol pentaacrylate and pentaacrylate ester. Other examples of cross-linking agents include: ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycoldi(meth)acrylate, tricyclodecanediyl-dimethylene di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth) acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, hexanediol diacrylate, 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, bis(2-methacryloxyethyl)N,N-1,9-nonylene biscarbamate, 1,4-cyclohexanedimethanol dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate pentaerythritol triacrylate, N,N′-methylenebisacrylamide, N,N′-methylenebisacrylamide, N,N′-(1,2-dihydroxyethylene)bisacrylamide, N-(1-hydroxy-2,2-dimethoxyethyl)acrylamide, divinylbenzene, tris(trimethylsilyl)silane, 1,4-butanediol divinyl ether, benzyl acrylate, benzyl methacrylate, vinyl benzoate, N-acryloylmorpholine, 1,10-decanediol diacrylate, triethylene glycol dithiol, and combinations thereof.

With respect to the photoinitiators, in some embodiments, the radiation source employed for initiating the polymerization is selected based on the type of photoinitiator used. Generally, the photoinitiator is a chemical compound that decomposes into free radicals when exposed to light but cationic photoinitiators may be used as well. There are a number of photoinitiators known in the art. For example, suitable photoinitiators include, but are not limited to, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 7-diethylamino-2-coumarin, acetophenone, p-tert-butyltrichloro acetophenone, chloro acetophenone, 2-2-diethoxy acetophenone, hydroxy acetophenone, 2,2-dimethoxy-2′-phenyl acetophenone, 2-amino acetophenone, dialkylamino acetophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoyl benzoate, methyl-o-benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, hydroxypropyl benzophenone, acrylic benzophenone, 4-4′-bis(dimethylamino)benzophenone, perfluoro benzophenone, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, diethyl thioxanthone, dimethyl thioxanthone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amyl anthraquinone, acetophenone dimethyl ketal, benzyl dimethyl ketal, α-acyl oxime ester, benzyl-(o-ethoxycarbonyl)-α-monoxime, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(4-methoxybenzoyl) diethylgermanium, tetrabenzoylgermane, tetramesitoylgermane, glyoxy ester, 3-keto coumarin, 2-ethyl anthraquinone, camphor quinone, tetramethylthiuram sulfide, azo bis isobutyl nitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxy pivalate, perfluoro tert-butyl peroxide, perfluoro benzoyl peroxide, triarylsulfonium hexafluoroantimonate salts, etc. Further, it is possible to use these photoinitiator alone or in combination of two or more.

A skilled person would understand a suitable amount of photoinitiator(s) that may be used to initiate a photopolymerization reaction herein. One embodiment includes less than about 0.5% by weight of the at least one photoinitiator based on the weight of the homogeneous mixture. In some embodiments, the amount is less than about 0.4% by weight, less than about 0.3% by weight, or less than about 0.1% by weight based on the weight of the homogeneous mixture.

With respect to the amount of the at least one photoinitiator that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes less than about 3% by weight of the at least one photoinitiator. In some embodiments, the amount is less than about 3% by weight, less than about 1.8% by weight, less than about 1.5% by weight, or less than about 1% by weight based on the weight of based on the weight of the at least one polymerizable component (e.g. resin).

With respect to the photosensitizers, in some embodiments, the photosensitizers are used to initiate polymerization (e.g. may initiate formation of free radicals from a photoinitiator). There are a number of photosensitizers known in the art. A skilled person would understand a suitable amount of photosensitizers that may be used to initiate a photopolymerization reaction. For example, suitable photosensitizers include, but are not limited to, isopropyl-9H-thioxanthen-9-one, anthracene, phenothiazine, perylene, thioxanthone, benzophenone, acetophenone, pyrene, acridinedione, boron-dipyrromethenes, curcumin, coumarin, etc.

It is understood that various ratios of the components may be used in the method of making the product. Depending on the ratios, different functional products result. For example, with respect to a larger proportion of photoinitiator, the method may form more radicals causing a larger concentration of the monomers to polymerize quickly, forming a more fragile product. With respect to larger amounts of monomer compared to cross-linking agent, fewer points of branching may result in a product with higher fragility. An excess of cross-linking agent may also cause the monomer to gel quickly, creating an inelastic structure. In examples, higher cross-linking agent percentages may provide products having greater tensile strength and lower cross-linking agent percentages may provide products having lower resistivities. In certain examples, higher cross-linking agent percentages may provide products having greater tensile strength with graded and composite products and lower cross-linking agent percentages may provide products having lower resistivities with functionally coated phase separated products.

With respect to the ratios of the components of the at least one polymerizable component, any suitable ratios can be used depending on the desired functional and/or functional precursor product. With respect to the at least one polymerizable component comprising at least one monomer and at least one cross-linking agent, in embodiments, the ratio of the at least one monomer to at least one cross-linking agent includes about 9:1 to about 0:10 based on % by weight. In some embodiments, the amount is about 9:1 to about 1:9 based on % by weight, about 8:2 to about 2:8 based on % by weight, about 7:3 to about 3:7 based on % by weight, about 6:4 to about 4:6 based on % by weight, about 5:5 to about 5:5 based on % by weight, about 4:6 to about 6:4 based on % by weight, about 3:7 to about 7:3 based on % by weight, about 2:8 to about 8:2 based on % by weight, or about 1:10 to about 9:1 based on % by weight.

With respect to the at least one polymerizable component comprising at least one monomer, at least one cross-linking agent, and at least one photoinitiator, in embodiments, the ratio of the at least one monomer to at least one cross-linking agent to at least one photoinitiator includes about 8.9:1:0.1 to about 0:9.9:0.1 based on % by weight.

To design functional products, and tune the chemical and/or physical properties, the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components may be leveraged to control the placement of functional components. When components have similar hydrophilic or hydrophobic properties, the components will have less of a driving force to phase separate upon polymerization. If the components differ in their hydrophobicity or hydrophilicity, the functional component will have a larger driving force to separate from the composition (e.g. substantially homogenous polymerizing monomer/cross-linking agent composition/mixture). The resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.

Upon polymerization of the at least one first polymerizable component, the at least one first component can separate and migrate towards a region where the concentration of the at least one first polymerizable component is greater (which may be slowly decreasing with polymerization) and the at least one second polymerizable component is greater and forms a composite coating of, mostly, the first component and the at least one second polymerizable component. With further polymerization of the at least one second polymerizable component, the at least one first component can separate and migrate towards a region where the concentration of the at least one second polymerizable component is greater and forms a coating of the first component.

In embodiments, the product comprises at least about 0.1% by weight of the at least one first component, or at least about 1% by weight of the at least one first component, or at least about 3% by weight of the at least one first component, or at least about 5% by weight of the at least one first component, or at least about 7% by weight of the at least one first component, or at least about 10% by weight of the at least one first component, or at least about 15% by weight of the at least one first component, or at least about 20% by weight of the at least one first component, or at least about 25% by weight of the at least one first component, or at least about 30% by weight of the at least one first component, based on the total weight of the product. In typical embodiments, the product comprises about 0.1 wt % to about 30 wt % by weight of the at least one first component, or about 3 wt % to about 25 wt % by weight of the at least one first component, or about 5 wt % to about 20 wt % by weight of the at least one first component, or about 5 wt % to about 15 wt % by weight of the at least one first component, based on the total weight of the product. In typical embodiments, the product comprises a functional material. The functional material may be a functionally graded material (FGM). The FGM may be a functionally graded composite material (FGCM).

With respect to the at least one first component, in embodiments, the at least one first component is substantially soluble in the at least one first and/or second polymerizable component(s) and is substantially insoluble when the first and/or second polymerizable component(s) polymerizes. The at least one first component may be selected from the group consisting of functional monomers, functional polymers, metal precursors, carbon nanotubes (CNT), graphene, metal alloy precursors, metalloid precursors, and combinations thereof.

In embodiments, the at least one first component is at least one functional monomer. The at least one functional monomer may be fluorinated monomers such as, and without being limited thereto, fluorinated methacrylates. The fluorinated functional monomers may contribute hydrophobic properties to the functional product. In embodiments utilizing the functional monomer, the at least one polymerizable component is selectively polymerized (e.g. temperature/wavelength used) without substantially polymerizing the at least one functional monomer such that, for example, the functional monomer and the at least one polymer form at least two phases. In embodiments, the functional monomer may polymerize somewhat with the at least one first and/or second polymerizable component(s); however, at least two phases form.

In other embodiments, the at least one first component may be at least one functional polymer such as, and without being limited thereto, PEG. In embodiments utilizing the functional polymer, the at least one polymerizable component is polymerized such that, for example, the functional polymer and the at least one first and/or second polymerizable component(s) form at least two phases.

In embodiments, the at least one first component is selected from the group consisting of metal salts, metal coordination compounds, organometallic compounds, organometalloid compounds, and combinations thereof. In typical embodiments, the at least one first component is selected from the group consisting of metal salts, metalloid salts, and combinations thereof. In certain embodiments, the at least one first component is selected from the group consisting of metal carboxylates, metalloid carboxylates, and combinations thereof. The metal carboxylates may comprise from 1 to 20 carbon atoms, from 6 to 15 carbon atoms, or from 8 to 12 carbon atoms. The carboxylate group of the metal carboxylates may be an alkanoate. Examples of the at least one first component is selected from the group consisting of metal formate, metal acetate, metal propionate, metal butyrate, metal pentanoate, metal hexanoate, metal heptanoate, metal ethylhexanoate, metal behenate, metal benzoate, metal oleate, metal octanoate, metal nonanoate, metal decanoate, metal neodecanoate, metal hexafluoroacetylacetonate, metal phenylacetate, metal isobutyrylacetate, metal benzoylacetate, metal pivalate metal oxalate and combinations thereof.

With respect to the metal precursors: the metal ion may be selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, db³⁺, Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺ and alloys of any of the foregoing.

The at least one first component used in the method may be selected amongst nanoparticles and/or microparticles of at least one first component described herein. In certain embodiments, the nanoparticles and/or microparticles may be metal precursors such as metal ions, metal salts, metal oxides, and/or metal complexes which may be convertible to metal. More broadly, the at least one first component may be any suitable inorganic particle that can separate into at least two phases from the at least one polymer, including nanoparticles and/or microparticles.

In some embodiments, the nanoparticles or microparticles are composed of a metal or combinations of metals selected from metals of Groups IIA, IIIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB or IIB of block d of the Periodic Table of Elements. In other embodiments, said metallic nanoparticles or microparticles are selected from Ba, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Au, Pt, Pd, Ag, Mn, Co, Cd, Hf, Ta, Re, Os, Al, Sn, In, Ga, Ir, and combinations thereof. In some other embodiments, said metallic nanoparticles or microparticles are selected from Ba, Al, Cu, Ni, Ag, Au, Pt, Pd, Al, Fe, Co, Ti, Zn, In, Sn, Ga and combinations thereof. In yet other embodiments, said metallic nanoparticles or microparticles are selected from Al, Cu, Ni, Ti, Zn, Ag, and combinations thereof.

In some embodiments, said metallic nanoparticles or microparticles are selected from Ag, Cu, and Ag and Cu nanoparticles. In other embodiments, the metallic nanoparticles or microparticles are Ag nanoparticles. In some embodiments, the at least one first component is a metal precursor selected to be convertible in-situ into a metal by a chemical or electrochemical process. The metal precursor may also be reduced into corresponding metal by reduction of the metal precursor in the presence of a suitable photoinitiator and a radiation source. Thus, in some embodiments, the metal precursor is selected to be convertible into any one of the metals recited hereinabove. In some embodiments, the metal precursor is a salt form of any one metal recited hereinabove.

In some embodiments, the metal salt is comprised of an inorganic or organic anion and an inorganic or organic cation. In some embodiments, the anion is inorganic. Non-limiting examples of inorganic anions include HO⁻, F⁻, Cl⁻, Br⁻, I⁻, NO²⁻, NO³⁻, ClO⁴⁻, SO₄ ²⁻, SO₃ ⁻, PO⁴⁻ and CO₃ ²⁻. In some embodiments, the anion is organic. Non-limiting examples of organic anions include acetate (CH₃COO⁻), formate (HCOO⁻), citrate (C₃H₅O(COO)³⁻³) acetylacetonate, lactate (CH₃CH(OH)COO⁻), oxalate ((COO)²⁻²) and any derivative of the aforementioned. In some embodiments, the metal salt is not a metal oxide. In some embodiments, the metal salt is a metal oxide. In some embodiments, the metal salt is a salt of copper. Non-limiting examples of copper metal salts include copper formate, copper citrate, copper acetate, copper nitrate, copper acetylacetonate, copper perchlorate, copper chloride, copper sulfate, copper carbonate, copper hydroxide, copper sulfide or any other copper salt and the combinations thereof.

In some embodiments, the metal salt is a salt of nickel. Non-limiting examples of nickel metal salts include nickel formate, nickel citrate, nickel acetate, nickel nitrate, nickel acetylacetonate, nickel perchlorate, nickel chloride, nickel sulfate, nickel carbonate, nickel hydroxide or any other nickel salts and the combinations thereof.

In some embodiments, the metal salt is a salt of silver. Non-limiting examples of silver metal salts include silver carboxylates, silver lactate, silver nitrate, silver formate or any other silver salt and their mixtures. Typically, silver carboxylates may be used and comprise a silver ion and an organic group containing a carboxylate group. The carboxylate group may comprise from 1 to 20 carbon atoms, typically from 6 to 15 carbon atoms, more typically from 8 to 12 carbon atoms, for example 10 carbon atoms. The carboxylate group is typically an alkanoate. Some non-limiting examples of preferred silver carboxylates are silver ethylhexanoate, silver neodecanoate, silver benzoate, silver phenylacetate, silver isobutyrylacetate, silver benzoylacetate, silver oxalate, silver pivalate and any combinations thereof. In a typical embodiment, silver neodecanoate is used.

In other embodiments, the metal salt is selected from indium(II) acetate, indium(III) chloride, indium(III) nitrate; iron(II) chloride, iron(III) chloride, iron(II) acetate, gallium(III) acetylacetonate, gallium(II) chloride, gallium(II) chloride, gallium(II) nitrate; aluminum(III) chloride, aluminum(III) stearate; silver nitrate, silver chloride; dimethylzinc, diethylzinc, zinc chloride, tin(II) chloride, tin(IV) chloride, tin(II) acetylacetonate, tin(II) acetate; lead(II) acetate, lead(II) acetylacetonate, lead(II) chloride, lead(II) nitrate and PbS.

In other embodiments, the at least one first component is selected from metal oxides such as those mentioned above, including nanoparticles and/or microparticles. In certain embodiments, the metal oxides are selected from alumina, silica, barium titanate, transition metal oxides (e.g. zinc oxide, titanium oxide), and combinations thereof.

In other embodiments, the at least one first component is selected from nanowires, microparticles, nanoparticles, or combinations thereof, including any of the suitable at least one first component mentioned herein. In still other embodiments, the at least one first component comprises graphene.

With respect to the amount of the at least one first component, the amount of the at least one first component may be any suitable amount. For example, the amount may be from about 0.1% to about 90% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount of the at least one first component in the homogeneous mixture may be from about 0.1% to about 80% by weight, from about 0.1% to about 70% by weight, from about 0.1% to about 60% by weight, from about 0.1% to about 50% by weight, from about 0.1% to about 40% by weight, from about 0.1% to about 30% by weight, or from about 0.1% to about 20% by weight based on the weight of the homogeneous mixture.

In other embodiments of the method, various additives may be added. Additives can be included, for example, to increase the solubility of the at least one first component in the at least one polymer component. Various additives include, without being limited thereto, fillers, inhibitors, adhesion promoters, absorbers, dyes, pigments, anti-oxidants, carrier vehicles, heat stabilizers, flame retardants, thixotropic agents, flow control additives, dispersants, or combinations thereof. In typical embodiments, extending fillers, reinforcing fillers, dispersants, or combinations thereof are added. The additives can be microparticles or nanoparticles.

Products

In embodiments, there is provided a polymeric product made by the method described herein, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

As described herein, the method can provide spatially controlled functionality in a product. Such products may include, for example, improved mechanical or functional properties, controlled functionality with one step (3D printing), less material waste, less time consuming fabrication.

In an embodiment, a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one second polymerizable component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In another embodiment, a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one first component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product

In a further embodiment, a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one at least one polymer and/or polymer derivative, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In embodiments, there is provided a device comprising the product described herein. The device may be an electronic device. The electronic device may be selected from a conductor, a semiconductor, a thin film transistor, an electrode, photocell, circuit, and combinations thereof.

In embodiments, there is provided an article comprising the product described herein. The article may be wearable. The article may be a textile. The article may be a fibre, jewellery, ceramics, and the like.

The product described herein may be used for any one of catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices.

Formulations

In embodiments, there is provided a formulation for making a polymeric product. The formulation comprises a composition having at least one first polymerizable component and at least one second polymerizable component. The at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component. The product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product. In another embodiment, the at least one second polymerizable component is polymerizable to form at least one second polymer. In embodiments, the formulation described herein can be used to control the placement/positioning of components(s) and/or polymer(s) (e.g. spatial positioning, spatially controlled positioning, etc.). For example, the formulation can be used to provide selective positioning of component(s) and/or polymer(s) in a product (e.g. 2D or 3D structure). Therefore, the product may be designed such that specifically selected region(s) have one type of functionality and other region(s) have other type(s) of functionality. Such a formulation can provide spatially controlled functionality in the product. In such examples, the selected region(s) and unselected region(s) are near, adjacent, and/or coupled to each other. For instance, the first polymer(s) in the selected region(s) and the second polymer(s) in the unselected region(s) are near, adjacent, and/or coupled to each other.

In other embodiments, the formulation described herein can undergo orthogonal polymerization, different rates of polymerization, and/or have thermodynamic miscibility.

For example, with respect to orthogonal polymerization, each of the polymerization reactions proceed via different mechanisms. In a specific embodiment, a mechanism of a polymerization reaction of the at least one first polymerizable component is different from a mechanism of a polymerization reaction of the at least one second polymerizable component. Other embodiments may include as follows: a sequence of chemical reaction(s) of converting the at least one first polymerizable component (e.g. at least one first monomer and/or at least one first cross-linking agent) to the at least one first polymer, which differs from a sequence of chemical reaction(s) of converting the at least one second polymerizable component (e.g. at least one second monomer and/or at least one second cross-linking agent) to the at least one second polymer. The chemical reaction(s) may include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).

With respect to the different rates of polymerization, each of the polymerization reactions may proceed via different rates. For example, the rate of polymerizing the at least one first polymerizable component to form at least one first polymer is faster or slower than the rate of polymerizing the at least one second polymerizable component to form at least one second polymer. With respect to the rates of polymerization and in view of the different mechanisms of polymerization, certain monomer(s) that undergo radical polymerization may form polymers at a faster rate than other monomer(s) that undergo cationic polymerization. For example, (meth)acrylate-based monomers via radical polymerization may form polymers at a faster rate than epoxides via cationic polymerization. Different polymerization rates can also occur within the same mechanism of polymerization (e.g. radical polymerization). For example, acrylates tend to be more reactive in a radical polymerization reaction compared to a radical polymerization reaction with (meth)acrylates. In other embodiments, polymerization rates can increase with increasing monomer functionality, for example, from mono- to di- to tri-functional groups. In certain embodiments, the order of polymerization rates from fastest to slowest is tri-functionalized acrylates>di-functionalized acrylates>mono-functionalized acrylates>(meth)acrylates>epoxides. The at least one first and the at least one second polymerizable components may be selected from monomer(s)/crosslinker(s) of these categories.

With respect to the thermodynamic miscibility, each of the polymerization reactions may affect the thermodynamic miscibility. For example, thermodynamic miscibility of the at least one first polymer is different from thermodynamic miscibility of the at least one second polymer. In another example, with respect to a combination of the at least one first polymerizable component and the at least one second polymerizable component, as the at least one first polymerizable component (e.g. a first monomer and/or a first cross-linking agent) polymerizes to form the at least one first polymer, the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of the at least one second polymerizable component (e.g. a second monomer and/or a second cross-linking agent) in the polymer/monomer mixture, which causes phase separation. In other examples, the degree of phase separation can depend on the solubility and balance of intermolecular forces between each component (each of the first and second monomer(s)/cross-linking agent(s)). Incompatible functional groups in the polymerizable components can affect thermodynamic miscibility, such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.

These different mechanisms, rates of polymerization, and miscibilities are properties of the formulation that can control the placement/positioning of component(s) and/or polymer(s) within a product.

In the formulation, the composition has at least one first polymerizable component and at least one second polymerizable component. In an embodiment, the composition is a substantially homogeneous composition. In a further embodiment, the substantially homogeneous composition is a substantially homogeneous mixture.

The formulation is capable of achieving polymerization via initiation of polymerization in selected region(s) of the formulation, whereby such polymerization can induce phase separation. In embodiments, polymerization occurs in the selected region(s) to form a first polymer(s) and the unselected region(s) has the second polymerizable component(s). There may be some first polymerizable component(s) in the unselected region(s). The formulation may be contained in, for example, a reservoir prior to polymerization of the selected region(s).

In embodiments, the polymerizing may comprise photopolymerization (e.g. photoinduced polymerization). In another embodiment, the at least one first polymerizable component has at least one first monomer and/or at least one first cross-linking agent. In another embodiment, the at least one second polymerizable component has at least one second monomer and/or at least one second cross-linking agent. In embodiments, the formulation further comprises at least one photoinitiator. Polymerization may also occur via free-radical polymerization without a photoinitiator. With respect to polymerization, the polymerization may be achieved as described above under the many embodiments under the method section.

In another embodiment, the formulation comprises a first polymerizable component(s) and a second polymerizable component(s). The first polymerizable component(s) comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties. The second polymerizable component(s) comprises thermal curable monomer(s) and/or crosslinking agent(s) in suitable amounts to provide the desired optimal properties. The ratio of first polymerizable and second polymerizable component(s) was varied to optimize the phase separation and physical properties. The formulation of the first polymerizable component(s) and second polymerizable component(s) form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component(s), forming a 3D-printed polymer product having spaces or closed regions that confine, mostly, the second polymerizable component(s). The second polymerizable component(s) can be polymerized via thermal or UV curing. In this embodiment, phase separation can occur due to orthogonal polymerization mechanisms and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s). In one example, the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component and the second polymerizable component.

In a certain embodiment, the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that are substantially free of the “hard” polymer (e.g. spaces) but including the “soft” polymer resin. The “hard” polymer product can be heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having closed regions that are substantially free of the “hard” polymer (e.g. spaces) but trap the “soft” polymer resin (e.g. resin filled closed regions). The “hard” polymer product having the confined “soft” polymer resin can be heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the formulation comprises a first polymerizable component(s) and a second polymerizable component(s). The first polymerizable component(s) comprise monomer(s) and/or cross-linking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties. The second polymerizable component(s) comprises monomer(s) and/or crosslinker(s), and photoinitiator(s) in suitable amounts to provide the desired optimal properties. The ratio of the first polymerizable and second polymerizable components was varied to optimize the phase separation and physical properties. The formulation of first polymerizable component(s) and second polymerizable component(s) form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component polymer resin, forming a 3D-printed polymer product having closed regions that confine, mostly, the second polymerizable component(s). The second polymerizable component are polymerizable via thermal or UV curing. In this embodiment, phase separation occurs due to orthogonal polymerization mechanisms, different rates of polymerization, and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s). In one example, the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component(s) and the second polymerizable component(s).

In another embodiment, the formulation comprises a “soft” polymer resin and a “hard” polymerizable resin. The “soft” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The “hard” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The ratio of “soft” to “hard” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “soft” and “hard” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “soft” polymer resin, forming a “soft” polymer product (e.g. 3D-printed polymer product) having closed regions that confine mostly “hard” polymer resin and some “soft” polymer resin (e.g. resin filled closed regions). The “soft” polymer product having the confined “hard” polymer resin and some “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured). The final product comprises both “soft” and “hard” polymers.

In another embodiment, the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), one or both of which contains an epoxide functional group, and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide(s) resin (e.g. UV curable) or amine(s) resin (thermal curable) and a cationic initiator in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that include the “soft” polymer resin (e.g. filled regions). The “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to cause the pendent epoxide functional group of the 3D printed “hard” polymer to polymerize with the “soft” resin. The final product comprises both “soft” and “hard” polymers. Therefore, in embodiments, the formulation has first polymer(s) that may have at least one functional group that can react with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s). For example, the first polymer(s) are capable of bonding/tethering to the second polymer(s) and/or the second polymerizable component(s).

Therefore, in embodiments, the formulation comprises at least one first polymerizable component and at least one second polymerizable component to form a composition. The at least one first polymerizable component is polymerizable to form at least one first polymer, wherein at least two phases are formed from the at least one first polymer and the at least one second polymerizable component. The at least one second polymerizable component is polymerizable to form at least one second polymer, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product. The first polymer(s) may have at least one functional group that are capable of reacting with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s). For example, the first polymer(s) are bonded/tethered to the second polymer(s) and/or the second polymerizable component(s).

In another embodiment, the formulation comprises a “hard” polymer resin, a “soft” polymerizable resin and a photoinitiator. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), with slower kinetics and/or incompatible functional groups, in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product. Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs. non-polar, aromatic vs. aliphatic, or aliphatic vs. polydimethylsiloxane-functionalized). The “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin. The final product comprises both “soft” and “hard” polymers.

In another embodiment, the formulation comprises a “hard” polymer resin, a “soft” polymerizable resin, a photoinitiator, a cationic photoinitiator, and a photosensitizer. The “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The “soft” polymer resin has epoxide monomer(s) and epoxide crosslinking agent(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer. The ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties. The formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product. Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs. non-polar, aromatic vs. aliphatic, or aliphatic vs. polydimethylsiloxane-functionalized). The “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin. The final product comprises both “soft” and “hard” polymers.

In embodiments, the phase separation and architecture of the final 3D printed product may be defined by the kinetics, mechanisms of polymerization, and/or thermodynamic miscibility of the components and the patterned illumination of the 3D structure. The resulting unique structural motifs can create an overall product with different or improved physical/chemical properties. For example, alternating “hard” and “soft” phases (e.g. “hard” and “soft” polymers) improves the overall mechanical properties compared to similar structures of only the individual polymer. In another example, phase separated functional materials (e.g. first polymer(s) and second polymer(s)) allow certain regions to be conductive, responsive to external stimuli, etc.

Therefore, the first polymer(s) (e.g. formed from the first monomer(s) and/or the first cross-linking agent(s)) and the second polymer(s) (e.g. formed from the second monomer(s) and/or the second cross-linking agent(s)) can have different physical/chemical properties. For example, the first polymer(s) formed from polymerizing the first polymerizable component(s) may have mechanical properties that are characterized as “hard” or “soft”, while the second polymer(s) formed from polymerizing the slower, orthogonal and/or lower soluble second polymerizable component(s) may have mechanical properties that are characterized to be the opposite of the first polymer(s); “soft” or “hard”. In embodiments, a “hard” polymer may have the following mechanical properties: about 2000 to about 4000 MPa range in modulus of elasticity, about 40 to about 65 MPa range in tensile strength, and/or about 10 to about 25% range in elongation at break; a “soft” polymer may have the following mechanical properties: about 0.5 to about 5.0 MPa range in tensile strength and/or about 45 to about 250% range in elongation at break.

In other examples, the first polymer(s) and the second polymer(s) may be nanomaterials, dyes/pigments, conductive, tolerant, piezoelectric, responsive to external stimuli, and/or different environmental conditions, etc. External stimuli or environmental conditions can include temperature, pressure, surrounding environment (water or other chemicals), magnetic field, etc.

In another embodiment of a formulation, the formulation comprises a composition having at least one first polymerizable component and at least one polymer and/or polymer derivative thereof. The at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one polymer and/or polymer derivative thereof. The product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.

In a specific embodiment, the formulation comprises a composition having at least one first polymerizable component and a polymer and/or polymer derivative thereof. The at least one first polymerizable component is polymerizable to form a 3D printed first polymer structure, wherein two phases are formed from the 3D printed first polymer structure and the at least one polymer and/or polymer derivative thereof. The first polymerizable component comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties. The at least one polymer and/or polymer derivative thereof is capable of phase separating due to thermodynamic miscibility of the first polymerizable component and the at least one polymer and/or polymer derivative thereof. The ratio of first polymerizable component(s) and the at least one polymer and/or polymer derivative thereof may be varied to optimize the phase separation and desired resulting properties. The first polymerizable component(s) and the at least one polymer and/or polymer derivative thereof were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture). The mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component, forming a 3D-printed polymer structure in which the at least one polymer and/or polymer derivative thereof is either confined within the structure and phase separated out of the spaces or phase separated out of the 3D structure and into the spaces.

With respect to the amount of the at least one polymerizable component(s) that may be used in embodiments, any suitable amount can be used. One embodiment includes from about 10% to about 99% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 20% to about 99% by weight, from about 30% to about 99% by weight, from about 40% to about 99% by weight, from about 50% to about 99% by weight, from about 60% to about 99% by weight, from about 70% to about 99% by weight, or from about 80% to about 99% by weight based on the weight of the homogeneous mixture.

The product may be any suitable structure/object. The product may be a 3D- or 2D-product. In embodiments, the product is a film or a 3D-product. The product may have any desired geometry (e.g. shape). Various 3D structures and functional high aspect ratio coatings and functional patterns in devices, such as sensors, optoelectronic devices, solar cells, electrodes, RFID tags, antennas, electroluminescent devices, power sources and connectors for circuit boards may be fabricated. The product may have at least one functional property selected from the group consisting of chemical properties, mechanical properties, magnetic properties, optical properties, insulating or protective properties (e.g. towards heat, radiation, mechanical abrasion), properties, electrical properties, electrochemical, catalytic properties, and combinations thereof. In other embodiments, the product is at least one of stretchable, flexible, lightweight, porous, conductive, non-conductive, surface durable, increased surface area, hydrophobic, biocompatible, anti-bacterial, mould resistant, wear-resistant, heat resistant, cold resistant, improved surface properties (antifouling), reduce flame retardancy, and combinations thereof. In typical embodiments, the surface of the functional product (e.g. coating itself, coating of 3D-product, etc.) imparts the product with the functionality. In embodiments, the product is multifunctional and/or is a precursor product that is a precursor to a multifunctional product. The product may be used for various applications, including metal/semiconductor, catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices. Other embodiments of commercial uses for the product include, for example, metamaterials with millimetre wave communication devices, objects embedded with self-healing materials, 3D objects with responsive materials (ferrofluidics, piezoelectric materials, conductive channels, etc.) for soft robotics, shape recovery objects with controlled placement/positioning of actuation material, encryption or anti-counterfeiting with treatment of spatially controlled structures with fluorescent ink, and/or parts for structural electronics (sensors and energy devices) with spatially controlled placement/positioning of conductive material within an object.

In embodiments, the product is conductive. The product may be selected to be any suitable conductivity. For example, it may have a conductivity (e.g. resistance) of at least about 1 Ω/cm; at least about 2 Ω/cm; at least about 5 Ω/cm; at least about 10 Ω/cm; at least about 15 Ω/cm; or at least about 20 Ω/cm. In other examples, the conductivity may be from about 1 to about 50 Ω/cm; from about 2 to about 50 Ω/cm; from about 5 to about 50 Ω/cm; from about 10 to about 50 Ω/cm; from about 15 to about 50 Ω/cm; from about 20 to about 50 Ω/cm; from about 1 to about 40 Ω/cm; from about 2 to about 40 Ω/cm; from about 5 to about 40 Ω/cm; from about 10 to about 40 Ω/cm; from about 15 to about 40 Ω/cm; from about 20 to about 40 Ω/cm; from about 1 to about 30 Ω/cm; from about 2 to about 30 Ω/cm; from about 5 to about 30 Ω/cm; from about 10 to about 30 Ω/cm; from about 15 to about 30 Ω/cm; from about 20 to about 30 Ω/cm; from about 1 to about 25 Ω/cm; from about 2 to about 25 Ω/cm; from about 5 to about 25 Ω/cm; from about 10 to about 25 Ω/cm; from about 15 to about 25 Ω/cm; from about 20 to about 25 Ω/cm; from about 10 to about 23 Ω/cm; or about 18 to about 23 Ω/cm.

In an embodiment, the formulation described herein can further comprise at least one first component. The first component(s) comprises at least one functional component, at least one functional precursor component, or a combination thereof. In another embodiment, the at least one functional precursor component is capable of being converted into at least one second functional component. In an embodiment, the at least one second functional component is different from said at least one functional component. In another embodiment, the at least one second functional component is the same as the at least one functional component. The converting may comprise sintering and/or pyrolyzing, for example, as described above. In some embodiments, the at least one functional precursor component is capable of being converted into at least one second functional component via sintering. The sintering may be at least one of thermal sintering, UV-VIS radiation sintering, and laser sintering. In embodiments, sintering may occur during or after printing.

In embodiments, the formulation is capable of being sintered to form the product, pyrolyzed to form the product, or sintered and pyrolyzed to form the product. In more specific embodiments, sintering is thermal sintering, UV-VIS radiation sintering, laser sintering or any combination thereof. In typical embodiments, minimum thermal sintering temperatures are selected based on a minimum temperature for converting the functional precursor to the functional product. Maximum thermal sintering temperatures may be selected based on a maximum temperature that the functional precursor and/or the functional product may be heated to without causing substantive decomposition or degradation. With respect to thermal sintering, the temperature ranges include, but are not limited thereto, from about 50° C. to about 300° C., or about 50° C. to about 280° C., or about 100° C. to about 280° C., or about 100° C. to about 270° C., or about 150° C. to about 280° C., or about 160° C. to about 270° C., or about 180° C. to about 250° C., or about 230° C. to about 250° C. Thermal sintering may occur under air or under inert condition(s), such as nitrogen. Thermal sintering may be performed for a time in ranges of about 15 minutes to about 180 minutes, or about 30 minutes to about 120 minutes, or about 45 minutes to about 60 minutes. In typical embodiments, sintering occurs under nitrogen with about 500 ppm oxygen. With respect to UV-VIS radiation sintering, sintering energies may range from about 1 J/cm² to about 30 J/cm², or about 2 J/cm² to about 10 J/cm², or about 2.5 J/cm² to about 5 J/cm², or about 2.4 J/cm² to about 3.1 J/cm². In certain embodiments, the pulse widths are about 500 s to about 5000 s, or about 1000 s to about 4000 s, or about 2500 s to about 3000 s. In typical embodiments, UV-VIS radiation sintering occurs under air. With respect to pyrolyzing, the temperature ranges include, but are not limited thereto, from about 350° C. to about 1200° C., or about 400° C. to about 900° C., or about 600° C. to about 800° C., or about 700° C. to about 800° C. Pyrolyzing may be performed for a time in a range of about 1 to about 60 minutes. Pyrolyzing may occur under air or under inert condition(s), such as nitrogen.

In embodiments, the first and second polymer(s) have a weight average molecular weight of about 10,000 to about 10,000,000, or about 10,000 to about 5,000 000, or about 10,000 to about 1,000,000, or about 50,000 to about 1,000,000, or about 50,000 to about 500,000. It is understood that the weight average molecular weight may approach infinity and includes cross-linked polymeric network(s).

With respect to the at least one first and second polymerizable component(s), each, independently, may comprise at least one monomer and/or at least one oligomer. The at least one first and second polymerizable component(s) may comprise at least one liquid monomer and/or at least one liquid oligomer. In a certain embodiment, the at least one first polymerizable component and/or the at least one second polymerizable component comprises at least one resin. Some examples include resins based on epoxies, vinyl ethers, acrylates, urethane-acrylates, methacrylates, acrylamides, thiol-ene based resins, styrene, siloxanes, silicones, and any functionalized derivatives thereof (e.g. fluorinated methacrylates, PEG-functionalized methacrylates or epoxies). The at least one resin may comprise at least one commercial resin. In particular, typical examples of the at least one resin comprises at least one commercial resin for 3D printing such as, and without being limited thereto, 3D printing via photoactivation (e.g. stereolithographic (SLA) printing or digital light processing (DLP)). In further embodiments, the at least one resin may comprise at least one acrylate based-resin. The monomer resins may be elastomers or pre-ceramic polymers.

In embodiments, the monomers and oligomers are selected according to their physico-chemical and chemical properties, such as monomer viscosity and/or surface tension, and/or polymer elasticity and/or hardness, number of polymerizable groups, and according to the printing method and the polymerization reaction type, e.g., the radiation source or heat source of choice. With respect to elasticity or hardness, some embodiments include modulus value ranges of from about 0.1 MPa to about 8000 MPa. In some embodiments, the monomers are selected from acid containing monomers, acrylic monomers, amine containing monomers, cross-linking acrylic monomers, dual reactive acrylic monomers, epoxides/anhydrides/imides, fluorescent acrylic monomers, fluorinated acrylic monomers, high or low refractive index monomers, hydroxy containing monomers, mono and difunctional glycol oligomeric monomers, styrenic monomers, vinyl and ethenyl monomers. In some embodiments, the monomers can polymerize to yield conductive polymers such as polypyrole and polyaniline. In some embodiments, the at least one monomer is selected from dipentaerythnitol hexaacrylate (DPHA) and trimethylolpropane triacrylate (TMPTA). In some embodiments, the at least one oligomer is selected from the group consisting of acrylates and vinyl containing molecules.

In other embodiments, the monomer can be any monomeric compound having a functional group, such as an activatable photopolymerizable group (photoinduced polymerization) that can propagate, for example, carbon-carbon, carbon-oxygen, carbon-nitrogen, or carbon-sulfur bond formation. In certain embodiments, the monomer is selected from mono-functional monomers (e.g. monomers with one functional group). During polymerization, the radical of the monofunctional monomer is formed and it will react with other monomers present to form oligomers and polymers. The resultant oligomers and polymers can have different properties depending on its structure. Some monomers may be selected depending on their flexibility, viscosity, curing rate, reactivity or toxicity. In one embodiment, the monomer is polymerized to form a polyacrylate such as polymethylmethacrylate, an unsaturated polyester, a saturated polyester, a polyolefin (polyethylenes, polypropylenes, polybutylenes, and the like), an alkyl resin, an epoxy polymer, a polyamide, a polyimide, a polyetherimide, a polyamideimide, a polyesterimide, a polyesteramideimide, polyurethanes, polycarbonates, polystyrenes, polyphenols, polyvinylesters, polysilicones, polyacetals, cellulose acetates, polyvinylchlorides, polyvinylacetates, polyvinyl alcohols polysulfones, polyphenylsulfones, polyethersulfones, polyketones, polyetherketones, poyletheretherketones, polybenzimidazoles, polybenzoxazoles, polybenzthiazoles, polyfluorocarbones, polyphenylene ethers, polyarylates, cyanate ester polymers, polystyrenes, polyacrylamide, polyvinylethers, copolymers of two or more thereof, and the like. In other embodiments, polyacrylates include polyisobomylacrylate, polyisobornylmethacrylate, polyethoxyethoxyethyl acrylate, poly-2-carboxyethylacrylate, polyethylhexylacrylate, poly-2-hydroxyethylacrylate, poly-2-phenoxylethylacrylate, poly-2-phenoxyethylmethacrylate, poly-2-ethylbutylmethacrylate, poly-9-anthracenylmethyl methacrylate, poly-4-chlorophenylacrylate, polycyclohexylacrylate, polydicyclopentenyloxyethyl acrylate, poly-2-(N,N-diethylamino)ethyl methacrylate, poly-dimethylaminoeopentyl acrylate, poly-caprolactone 2-(methacryloxy)ethylester, and polyfurfurylmethacrylate, poly(ethylene glycol)methacrylate, polyacrylic acid and poly(propylene glycol)methacrylate.

Monomers that may be used, for example, include acrylic monomers such as monoacrylics, diacrylics, triacrylics, tetraacrylics, pentacrylics, etc. Examples of other monomers include ethyleneglycol methyl ether acrylate, N,N-diisobutyl-acrylamide, N-vinyl-pyrrolidone, (meth)acryloyl morpholine, 7-amino-3,7-dimethyloctyl, (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth)acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N,N-dimethyl (meth) acrylamide tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl(meth)acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono-(meth)acrylate, methyl triethylene diglycol (meth)acrylate, alkoxylated alkyl phenol acrylate, (poly)caprolactone acrylate ester from methylol-tetrahydrofuran, (poly)caprolactone acrylate ester from alkylol-dioxane, ethylene glycol phenyl ether acrylate, and methacryloxypropyl terminated polydimethylsiloxane.

Other monomers that may be used, for example, include epoxide monomers such as 3,4-epoxyclyclohexylmethyl 3,4-epoxycylcohexanecarboxylate, epoxycyclohexylethyl terminated polydimethylsiloxane, bisphenol A diglycidyl ether, allyl glycidyl ether, bis[4-(glycidyloxy)phenyl]methane, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclohexene oxide, dicyclopentadiene dioxide, 1,2,7,8-diepoxycyclooctane, 1,2,5,6-diepoxyoctane, styrene oxide, neopentyl glycol dilycidyl ether, glycidyl isopropyl ether, glycidyl 4-methoxyphenyl ether, 2-ethylhexyl glycidyl ether, (2,3-epoxypropyl)benzene, 1,2-epoxy-3-phenoxypropane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxyhexane, 1,27,8-diepoxyoctane, dilycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, and/or epoxycyclohexylethyl terminated polydimethylsiloxane.

With respect to the amount of the first and second monomer(s) that may be used in embodiments, any suitable amount can be used depending on the desired functional and/or functional precursor product. One embodiment includes from about 10% to about 99% by weight of the at least one monomer based on the weight of the composition. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.

With respect to the amount of the at least one monomer that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes from about 1% to about 90% by weight of the at least one monomer. In some embodiments, the amount is from about 1% to about 85% by weight, from about 1% to about 80% by weight, from about 1% to about 75% by weight, from about 5% to about 90% by weight, from about 10% to about 90% by weight, from about 15% to about 90% by weight, from about 20% to about 90% by weight, from about 25% to about 90% by weight, from about 35% to about 90% by weight, from about 40% to about 90% by weight, from about 45% to about 90% by weight, from about 5% to about 80% by weight, from about 10% to about 80% by weight, from about 15% to about 80% by weight, from about 20% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component.

With respect to the at least one cross-linking agent, it may be included in the formulation. Cross-linking agents may have one or more functional groups and, typically, have two or more functional groups (e.g. di-, tri-, tetra-, etc. functional cross-linking agents). In certain embodiments, the functional groups may be present at both ends of the cross-linking agent, forming branched polymerization, whereby the cross-linking agent may react with two or more polymers. In certain embodiments, a 2D product is formed with a monofunctional cross-linking agent and a 3D product is formed with a multifunctional cross-linking agent.

In embodiments, the morphology of a functional and/or functional precursor product (e.g. 3D printed product) may depend on the concentration (e.g. amount) of cross-linking agent. The concentration of the cross-linking agent may control the rate at which a polymer network forms. In one embodiment, when the cross-linking agent concentration is high, the rate at which the monomers form polymer networks (e.g. branched polymerization) are high. High rates of polymer network formation may limit the diffusion of slower reacting or non-polymerizing components and provide more uniform compositions such as composites in certain regions (e.g. portions) of the product. Conversely, in other embodiments, when cross-linking agent concentrations are low and the rates of polymer network formations are low, slower polymerizing monomers or non-polymerizing components (e.g. silver salt, nanoparticles, etc.) can diffuse towards regions where their solubilities are higher. Their solubilities may be higher towards the surface of the printed product, where the polymer concentration is low and the monomer concentration is high. Therefore, formulations with low cross-linking agent concentrations may lead to printed products (e.g. objects) where the slower polymerizing monomer or non-polymerizing component forms a coating in certain regions of the product. In other embodiments, intermediate cross-linking agent concentrations can generate graded compositions in certain regions of the product. In embodiments, therefore, the morphology of the functional and/or functional precursor product can be a function of cross-linking agent concentrations in compositions (e.g. substantially homogeneous composition or substantially homogeneous mixture) containing non-polymerizing functional and/or functional precursor components.

In embodiments, the amount of functional and/or functional precursor component at the surface of the functional and/or functional precursor product decreases with increased concentration of cross-linking agent. The concentration of functional and/or functional precursor component at the surface can determine the resistance value of the printed product. As the concentration of cross-linking agent increases, the resistance of the functional and/or functional precursor component at the surface (e.g. coating) increases in view of the lower concentration of the functional and/or functional precursor component at the surface.

With respect to the amount of the at least one cross-linking agent that may be used in embodiments, any suitable amount can be used depending on the desired functional and/or functional precursor product. For example, the amount of the at least one cross-linking agent can be used to tune the morphology of the functional and/or functional precursor product. One embodiment includes from about 10% to about 99% mol based on the composition. In some embodiments, the amount is from about 80% to about 99% mol, from about 85% to about 99% mol, from about 90% to about 99% mol, from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 35% to about 55% mol, from about 35% to about 50% mol, from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the composition.

With respect to the amount of the at least one cross-linking agent, based on the weight of the composition, that may be used in embodiments, any suitable amount can be used. One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.

With respect to the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes from about 10% to about 99% by weight of the at least one cross-linking agent. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).

In some embodiments, portions of the functional and/or functional precursor product are a composite. The amount of the at least one crosslinking agent used to make the product is from about 80% to about 99% mol, from about 85% to about 99% mol, or from about 90% to about 99% mol based on the mol of the homogeneous mixture. In other embodiments, the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent. In a typical embodiment, the at least one cross-linking agent comprises at least one difunctional cross-linking agent.

In some embodiments, portions of the functional and/or functional precursor product is graded and/or coated. The amount of the at least one crosslinking agent used to make the product is from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 35% to about 55% mol, from about 35% to about 50% mol, from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the homogeneous mixture. In other embodiments, the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent. In a typical embodiment, the at least one cross-linking agent comprises at least one difunctional cross-linking agent.

In some embodiments, portions of the functional and/or functional precursor product are graded. The amount of the at least one crosslinking agent used to make the product is from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 35% to about 55% mol, from about 35% to about 50% mol, from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the homogeneous mixture. In other embodiments, the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent.

In some embodiments, portions of the functional and/or functional precursor product are coated. The amount of the at least one crosslinking agent used to make the product is from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the homogeneous mixture. In other embodiments, the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent. In a typical embodiment, the at least one cross-linking agent comprises at least one difunctional cross-linking agent.

With respect to the amount of the at least one cross-linking agent, based on the weight of the homogenous mixture, that may be used in embodiments, any suitable amount can be used. One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the homogeneous mixture.

With respect to the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes from about 10% to about 99% by weight of the at least one cross-linking agent. In some embodiments, the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).

In embodiments, the cross-linking agent is a radical reactive cross-linking agent. Examples of the radical reactive cross-linking agent include a methacrylic compound, an acrylic compound, a vinyl compound, and an allyl compound. Examples of suitable cross-linking agents which can be used to form polyacrylates include 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, bis(2-methacryloxyethyl)N,N-1,9-nonylene biscarbamate, 1,4-cyclohexanedimethanol dimethacrylate, and diacrylic urethane oligomers (reaction products of isocyanate terminate polyol and 2-hydroethylacrylate). Examples of triacrylates which can be used to form polyacrylates include tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. Examples of tetracrylates include pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, and ethoxylated pentaerythritol tetraacrylate. Examples of pentaacrylates include dipentaerythritol pentaacrylate and pentaacrylate ester. Other examples of cross-linking agents include: ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycoldi(meth)acrylate, tricyclodecanediyl-dimethylene di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth) acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, hexanediol diacrylate, 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, bis(2-methacryloxyethyl)N,N-1,9-nonylene biscarbamate, 1,4-cyclohexanedimethanol dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate pentaerythritol triacrylate, N,N′-methylenebisacrylamide, N,N′-methylenebisacrylamide, N,N′-(1,2-dihydroxyethylene)bisacrylamide, N-(1-hydroxy-2,2-dimethoxyethyl)acrylamide, divinylbenzene, tris(trimethylsilyl)silane, 1,4-butanediol divinyl ether, benzyl acrylate, benzyl methacrylate, vinyl benzoate, N-acryloylmorpholine, 1,10-decanediol diacrylate, triethylene glycol dithiol, and combinations thereof.

With respect to the photoinitiators, in some embodiments, the radiation source employed for initiating the polymerization is selected based on the type of photoinitiator used. Generally, the photoinitiator is a chemical compound that decomposes into free radicals when exposed to light but cationic photoinitiators may be used as well. There are a number of photoinitiators known in the art. For example, suitable photoinitiators include, but are not limited to, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 7-diethylamino-2-coumarin, acetophenone, p-tert-butyltrichloro acetophenone, chloro acetophenone, 2-2-diethoxy acetophenone, hydroxy acetophenone, 2,2-dimethoxy-2′-phenyl acetophenone, 2-amino acetophenone, dialkylamino acetophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoyl benzoate, methyl-o-benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, hydroxypropyl benzophenone, acrylic benzophenone, 4-4′-bis(dimethylamino)benzophenone, perfluoro benzophenone, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, diethyl thioxanthone, dimethyl thioxanthone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amyl anthraquinone, acetophenone dimethyl ketal, benzyl dimethyl ketal, α-acyl oxime ester, benzyl-(o-ethoxycarbonyl)-α-monoxime, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(4-methoxybenzoyl) diethylgermanium, tetrabenzoylgermane, tetramesitoylgermane, glyoxy ester, 3-keto coumarin, 2-ethyl anthraquinone, camphor quinone, tetramethylthiuram sulfide, azo bis isobutyl nitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxy pivalate, perfluoro tert-butyl peroxide, perfluoro benzoyl peroxide, triarylsulfonium hexafluoroantimonate salts, etc. Further, it is possible to use these photoinitiator alone or in combination of two or more.

A skilled person would understand a suitable amount of photoinitiator(s) that may be used to initiate a photopolymerization reaction herein. One embodiment includes less than about 0.5% by weight of the at least one photoinitiator based on the weight of the homogeneous mixture. In some embodiments, the amount is less than about 0.4% by weight, less than about 0.3% by weight, or less than about 0.1% by weight based on the weight of the homogeneous mixture.

With respect to the amount of the at least one photoinitiator that may be used in embodiments based on the weight of the at least one polymerizable component itself, includes less than about 3% by weight of the at least one photoinitiator. In some embodiments, the amount is less than about 3% by weight, less than about 1.8% by weight, less than about 1.5% by weight, or less than about 1% by weight based on the weight of based on the weight of the at least one polymerizable component (e.g. resin).

With respect to the photosensitizers, in some embodiments, the photosensitizers are used to initiate polymerization (e.g. may initiate formation of free radicals from a photoinitiator). There are a number of photosensitizers known in the art. A skilled person would understand a suitable amount of photosensitizers that may be used to initiate a photopolymerization reaction. For example, suitable photosensitizers include, but are not limited to, isopropyl-9H-thioxanthen-9-one, anthracene, phenothiazine, perylene, thioxanthone, benzophenone, acetophenone, pyrene, acridinedione, boron-dipyrromethenes, curcumin, coumarin, etc.

It is understood that various ratios of the components may be used in the formulation for making the product. Depending on the ratios, different functional products result. For example, with respect to a larger proportion of photoinitiator, more radicals may form causing a larger concentration of the monomers to polymerize quickly, forming a more fragile product. With respect to larger amounts of monomer compared to cross-linking agent, fewer points of branching may result in a product with higher fragility. An excess of cross-linking agent may also cause the monomer to gel quickly, creating an inelastic structure. In examples, higher cross-linking agent percentages may provide products having greater tensile strength and lower cross-linking agent percentages may provide products having lower resistivities. In certain examples, higher cross-linking agent percentages may provide products having greater tensile strength with graded and composite products and lower cross-linking agent percentages may provide products having lower resistivities with functionally coated phase separated products.

With respect to the ratios of the components of the at least one polymerizable component, any suitable ratios can be used depending on the desired functional and/or functional precursor product. With respect to the at least one polymerizable component comprising at least one monomer and at least one cross-linking agent, in embodiments, the ratio of the at least one monomer to at least one cross-linking agent includes about 9:1 to about 0:10 based on % by weight. In some embodiments, the amount is about 9:1 to about 1:9 based on % by weight, about 8:2 to about 2:8 based on % by weight, about 7:3 to about 3:7 based on % by weight, about 6:4 to about 4:6 based on % by weight, about 5:5 to about 5:5 based on % by weight, about 4:6 to about 6:4 based on % by weight, about 3:7 to about 7:3 based on % by weight, about 2:8 to about 8:2 based on % by weight, or about 1:10 to about 9:1 based on % by weight.

With respect to the at least one polymerizable component comprising at least one monomer, at least one cross-linking agent, and at least one photoinitiator, in embodiments, the ratio of the at least one monomer to at least one cross-linking agent to at least one photoinitiator includes about 8.9:1:0.1 to about 0:9.9:0.1 based on % by weight.

To design functional products, and tune the chemical and/or physical properties, the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components may be leveraged to control the placement of functional components. When components have similar hydrophilic or hydrophobic properties, the components will have less of a driving force to phase separate upon polymerization. If the components differ in their hydrophobicity or hydrophilicity, the functional component will have a larger driving force to separate from the composition (e.g. substantially homogenous polymerizing monomer/cross-linking agent composition/mixture). The resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.

Upon polymerization of the at least one first polymerizable component, the at least one first component can separate and migrate towards a region where the concentration of the at least one first polymerizable component is greater (which may be slowly decreasing with polymerization) and the at least one second polymerizable component is greater and forms a composite coating of, mostly, the first component and the at least one second polymerizable component. With further polymerization of the at least one second polymerizable component, the at least one first component can separate and migrate towards a region where the concentration of the at least one second polymerizable component is greater and forms a coating of the first component.

In embodiments, the product comprises at least about 0.1% by weight of the at least one first component, or at least about 1% by weight of the at least one first component, or at least about 3% by weight of the at least one first component, or at least about 5% by weight of the at least one first component, or at least about 7% by weight of the at least one first component, or at least about 10% by weight of the at least one first component, or at least about 15% by weight of the at least one first component, or at least about 20% by weight of the at least one first component, or at least about 25% by weight of the at least one first component, or at least about 30% by weight of the at least one first component, based on the total weight of the product. In typical embodiments, the product comprises about 0.1 wt % to about 30 wt % by weight of the at least one first component, or about 3 wt % to about 25 wt % by weight of the at least one first component, or about 5 wt % to about 20 wt % by weight of the at least one first component, or about 5 wt % to about 15 wt % by weight of the at least one first component, based on the total weight of the product. In typical embodiments, the product comprises a functional material. The functional material may be a functionally graded material (FGM). The FGM may be a functionally graded composite material (FGCM).

With respect to the at least one first component, in embodiments, the at least one first component is substantially soluble in the at least one first and/or second polymerizable component(s) and is substantially insoluble when the first and/or second polymerizable component(s) polymerizes. The at least one first component may be selected from the group consisting of functional monomers, functional polymers, metal precursors, carbon nanotubes (CNT), graphene, metal alloy precursors, metalloid precursors, and combinations thereof.

In embodiments, the at least one first component is at least one functional monomer. The at least one functional monomer may be fluorinated monomers such as, and without being limited thereto, fluorinated methacrylates. The fluorinated functional monomers may contribute hydrophobic properties to the functional product. In embodiments utilizing the functional monomer, the at least one polymerizable component is selectively polymerized (e.g. temperature/wavelength used) without substantially polymerizing the at least one functional monomer such that, for example, the functional monomer and the at least one polymer form at least two phases. In embodiments, the functional monomer may polymerize somewhat with the at least one first and/or second polymerizable component(s); however, at least two phases form.

In other embodiments, the at least one first component may be at least one functional polymer such as, and without being limited thereto, PEG. In embodiments utilizing the functional polymer, the at least one polymerizable component is polymerized such that, for example, the functional polymer and the at least one first and/or second polymerizable component(s) form at least two phases.

In embodiments, the at least one first component is selected from the group consisting of metal salts, metal coordination compounds, organometallic compounds, organometalloid compounds, and combinations thereof. In typical embodiments, the at least one first component is selected from the group consisting of metal salts, metalloid salts, and combinations thereof. In certain embodiments, the at least one first component is selected from the group consisting of metal carboxylates, metalloid carboxylates, and combinations thereof. The metal carboxylates may comprise from 1 to 20 carbon atoms, from 6 to 15 carbon atoms, or from 8 to 12 carbon atoms. The carboxylate group of the metal carboxylates may be an alkanoate. Examples of the at least one first component is selected from the group consisting of metal formate, metal acetate, metal propionate, metal butyrate, metal pentanoate, metal hexanoate, metal heptanoate, metal ethylhexanoate, metal behenate, metal benzoate, metal oleate, metal octanoate, metal nonanoate, metal decanoate, metal neodecanoate, metal hexafluoroacetylacetonate, metal phenylacetate, metal isobutyrylacetate, metal benzoylacetate, metal pivalate metal oxalate and combinations thereof.

With respect to the metal precursors: the metal ion may be selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁺, Zr³⁺, Zr²⁺, Hf⁴⁺, Hf³⁺, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵, Mo⁴, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co Co⁴⁺, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺, B⁺, Al⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶, Te⁵, Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, db³⁺, db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Yb²⁺, Lu³⁺ and alloys of any of the foregoing.

The at least one first component used in the method may be selected amongst nanoparticles and/or microparticles of at least one first component described herein. In certain embodiments, the nanoparticles and/or microparticles may be metal precursors such as metal ions, metal salts, metal oxides, and/or metal complexes which may be convertible to metal. More broadly, the at least one first component may be any suitable inorganic particle that can separate into at least two phases from the at least one polymer, including nanoparticles and/or microparticles.

In some embodiments, the nanoparticles or microparticles are composed of a metal or combinations of metals selected from metals of Groups IIA, IIIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB or IIB of block d of the Periodic Table of Elements. In other embodiments, said metallic nanoparticles or microparticles are selected from Ba, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Au, Pt, Pd, Ag, Mn, Co, Cd, Hf, Ta, Re, Os, Al, Sn, In, Ga, Ir, and combinations thereof. In some other embodiments, said metallic nanoparticles or microparticles are selected from Ba, Al, Cu, Ni, Ag, Au, Pt, Pd, Al, Fe, Co, Ti, Zn, In, Sn, Ga and combinations thereof. In yet other embodiments, said metallic nanoparticles or microparticles are selected from Al, Cu, Ni, Ti, Zn, Ag, and combinations thereof.

In some embodiments, said metallic nanoparticles or microparticles are selected from Ag, Cu, and Ag and Cu nanoparticles. In other embodiments, the metallic nanoparticles or microparticles are Ag nanoparticles. In some embodiments, the at least one one first component is a metal precursor selected to be convertible in-situ into a metal by a chemical or electrochemical process. The metal precursor may also be reduced into corresponding metal by reduction of the metal precursor in the presence of a suitable photoinitiator and a radiation source. Thus, in some embodiments, the metal precursor is selected to be convertible into any one of the metals recited hereinabove. In some embodiments, the metal precursor is a salt form of any one metal recited hereinabove.

In some embodiments, the metal salt is comprised of an inorganic or organic anion and an inorganic or organic cation. In some embodiments, the anion is inorganic. Non-limiting examples of inorganic anions include HO⁻, F⁻, Cl⁻, Br⁻, I⁻, NO₂ ⁻, NO₃ ⁻, ClO₄ ⁻, SO₄ ²⁻, SO₃ ⁻, PO₄ ⁻ and CO₃ ²⁻. In some embodiments, the anion is organic. Non-limiting examples of organic anions include acetate (CH₃COO⁻), formate (HCOO⁻), citrate (C₃H₅O(COO)₃ ⁻³) acetylacetonate, lactate (CH₃CH(OH)COO⁻), oxalate ((COO)₂ ⁻²) and any derivative of the aforementioned. In some embodiments, the metal salt is not a metal oxide. In some embodiments, the metal salt is a metal oxide. In some embodiments, the metal salt is a salt of copper. Non-limiting examples of copper metal salts include copper formate, copper citrate, copper acetate, copper nitrate, copper acetylacetonate, copper perchlorate, copper chloride, copper sulfate, copper carbonate, copper hydroxide, copper sulfide or any other copper salt and the combinations thereof.

In some embodiments, the metal salt is a salt of nickel. Non-limiting examples of nickel metal salts include nickel formate, nickel citrate, nickel acetate, nickel nitrate, nickel acetylacetonate, nickel perchlorate, nickel chloride, nickel sulfate, nickel carbonate, nickel hydroxide or any other nickel salts and the combinations thereof.

In some embodiments, the metal salt is a salt of silver. Non-limiting examples of silver metal salts include silver carboxylates, silver lactate, silver nitrate, silver formate or any other silver salt and their mixtures. Typically, silver carboxylates may be used and comprise a silver ion and an organic group containing a carboxylate group. The carboxylate group may comprise from 1 to 20 carbon atoms, typically from 6 to 15 carbon atoms, more typically from 8 to 12 carbon atoms, for example 10 carbon atoms. The carboxylate group is typically an alkanoate. Some non-limiting examples of preferred silver carboxylates are silver ethylhexanoate, silver neodecanoate, silver benzoate, silver phenylacetate, silver isobutyrylacetate, silver benzoylacetate, silver oxalate, silver pivalate and any combinations thereof. In a typical embodiment, silver neodecanoate is used.

In other embodiments, the metal salt is selected from indium(II) acetate, indium(III) chloride, indium(III) nitrate; iron(II) chloride, iron(III) chloride, iron(II) acetate, gallium(III) acetylacetonate, gallium(II) chloride, gallium(II) chloride, gallium(II) nitrate; aluminum(III) chloride, aluminum(III) stearate; silver nitrate, silver chloride; dimethylzinc, diethylzinc, zinc chloride, tin(II) chloride, tin(IV) chloride, tin(II) acetylacetonate, tin(II) acetate; lead(II) acetate, lead(II) acetylacetonate, lead(II) chloride, lead(II) nitrate and PbS.

In other embodiments, the at least one first component is selected from metal oxides such as those mentioned above, including nanoparticles and/or microparticles. In certain embodiments, the metal oxides are selected from alumina, silica, barium titanate, transition metal oxides (e.g. zinc oxide, titanium oxide), and combinations thereof.

In other embodiments, the at least one first component is selected from nanowires, microparticles, nanoparticles, or combinations thereof, including any of the suitable at least one first component mentioned herein. In still other embodiments, the at least one first component comprises graphene.

With respect to the amount of the at least one first component, the amount of the at least one first component may be any suitable amount. For example, the amount may be from about 0.1% to about 90% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount of the at least one first component in the homogeneous mixture may be from about 0.1% to about 80% by weight, from about 0.1% to about 70% by weight, from about 0.1% to about 60% by weight, from about 0.1% to about 50% by weight, from about 0.1% to about 40% by weight, from about 0.1% to about 30% by weight, or from about 0.1% to about 20% by weight based on the weight of the homogeneous mixture.

In other embodiments of the method, various additives may be added. Additives can be included, for example, to increase the solubility of the at least one first component in the at least one polymer component. Various additives include, without being limited thereto, fillers, inhibitors, adhesion promoters, absorbers, dyes, pigments, anti-oxidants, carrier vehicles, heat stabilizers, flame retardants, thixotropic agents, flow control additives, dispersants, or combinations thereof. In typical embodiments, extending fillers, reinforcing fillers, dispersants, or combinations thereof are added. The additives can be microparticles or nanoparticles.

In embodiments, the formulation may be used to make the product described herein.

Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize and practice the claimed products, formulations and methods. A more complete understanding can be obtained by reference to the following specific examples. These examples are provided for purposes of illustration only, and are not intended to be limiting. Thus, the invention should in no way be construed as being limited to the following examples, but rather, should be construed to encompass any and all variations which become evident as a result of the teaching provided in the disclosure. The following working examples therefore, specifically point out aspects, and are not to be construed as limiting in any way.

EXAMPLES

Below is a list of abbreviations used to denote various chemical components of the formulations.

Abbreviations

Ethylene glycol diacrylate EGDA 2-Ethylhexyl acrylate EHA Ethyl (2,4,6-trimethylbenzoyl) TPO-L phenylphosphinate Silver neodecanoate AgND 2-Ethyl-2-oxazoline EtOxa Polyethyleneglycol diacrylate Mn 250* PEGDA250 Tetraethyleneglycol diacrylate TEGDA Polyethyleneglycol diacrylate Mn 575* PEGDA575 Polyethyleneglycol diacrylate Mn 700* PEGDA700 1,4-Butanediol diacrylate BDDA 1,6-Hexanediol diacrylate HDDA Ethylene glycol methyl ether acrylate EGMEA Di(trimethylolpropane) tetraacrylate DTMPTA *Mn is the number average molecular mass in g/mol

Formulation Examples 1-15

Examples 1-15 illustrate the various compositions and printing considerations for the making of conductive products (e.g. electrical devices) and non-conductive products (e.g. consumer products where it is desirable to have decorative coatings, such as jewellery).

Comparative Example 1: Coating of SLA Printed Acrylate-Based Resin (FSL 3D) 3D Product with Ag Precursor i.e. Silver Neodecanoate+2-Ethyl-2-Oxazoline_7% Ag Metal

Commercial acrylate-based resin (Pegasus, FSL3D) was printed into cylinders about 1 cm in length and about 1 mm in diameter using a SLA printer and then immersed in a mixture of Ag precursor composed of about 4.44 g silver neodecanoate+about 20.084 ml 2-ethyl-2-oxazoline (7% Ag metal). Coated 3D products were thermally sintered by using a reflow oven program to heat between about 200 and about 250° C. temperature for varying times under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 μs under ambient conditions.

Example 2: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_1.97% Ag Metal)

A resin was formulated by mixing about 6.25 g silver neodecanoate+about 1.38 ml 2-ethyl-2-oxazoline+about 114.99 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 1.97 wt. % silver content. The resin was printed into cylinders about 1 cm in length and about 1 mm in diameter. The 3D products were thermally sintered by using a reflow oven program to heat from about 200 to about 250° C. temperature for varying times under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 3: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_3.84% Ag Metal)

A resin was formulated by mixing about 12.5 g silver neodecanoate+about 2.76 ml 2-ethyl-2-oxazoline+about 107.36 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 3.84 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 4: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_7% Ag Metal)

A resin was formulated by mixing about 22.2 g silver neodecanoate+about 5.03 ml 2-ethyl-2-oxazoline+about 94.89 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 5: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_7.9% Ag Metal)

A resin was formulated by mixing about 25 g silver neodecanoate+about 5.52 ml 2-ethyl-2-oxazoline+about 92.1 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7.9 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 6: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_9.85% Ag Metal)

A resin was formulated by mixing about 31.25 g silver neodecanoate+about 6.9 ml 2-ethyl-2-oxazoline+about 84.47 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 9.85 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 7: SLA Printed Ag Salt+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate_7% Ag Metal)

A resin was formulated by mixing about 22.2 g silver neodecanoate+about 100.42 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered between about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 8: Ag Precursor+(10% TMPTA, 89% EtHex Acrylate) Resin

About 1.00 g of trimethylolpropane triacrylate, about 8.90 g of 2-ethylhexylacrylate, and about 0.10 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 240 to about 300° C. temperature ranges (program) for about 1 hour using reflow oven under nitrogen.

Example 9: Ag Precursor+(99% TMPTA) Resin

About 9.90 g of trimethylolpropane triacrylate and about 0.10 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 1 minute. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 10: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Nitrate+2-Ethyl-2-Oxazoline_7% Ag Metal)

A resin was formulated by mixing about 13.5 g silver nitrate+about 6.04 ml 2-ethyl-2-oxazoline+about 103.73 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 11: SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Acetate+2-Ethyl-2-Oxazoline_7% Ag Metal)

A resin was formulated by mixing about 13.3 g silver acetate+about 8.05 ml 2-ethyl-2-oxazoline+about 101.29 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 12: SLA Printed Cu Precursor+Acrylate-Based Resin (FSL 3D) (Cu Formate+_7% Cu Metal)

A resin was formulated by mixing about 23.18 g copper formate hydrate+about 10.3 ml 3-(diethylamino)-1 2-propanediol+about 89.15 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % Cu content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm² for about 3000 s under ambient conditions.

Example 13: SLA Printed Graphene+Acrylate-Based Resin (FSL 3D) (0.05% Graphene)

A resin was formulated by mixing about 0.05 g graphene (N002-PDR-HD Angstrom Materials)+about 1.25 g dispersant BYK 180+about 98.7 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 0.05 wt. % graphene content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 200° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 14: SLA Printed Graphene+Acrylate-Based Resin (FSL 3D) (0.4% Graphene)

A resin was formulated by mixing about 0.4 g graphene (N002-PDR-HD Angstrom Materials)+about 10 g dispersant BYK 180+about 89.6 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with 0.4 wt. % graphene content. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 200° C. (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Formulation of Silver Particle and Graphene 3D Printable Resins:

Submicron silver particles and different amounts of graphene were dissolved in a dispersant BYK 180 and then mixed with commercial acrylate-based resin (Pegasus, FSL3D).

Example 15: SLA Printing of Hydrophobic Tiles Using Fluorinated Monomers

Resins containing various % weight of 1H,1H-perfluorooctyl methacrylate, 2-ethylhexyl acrylate and trimethylolpropane triacrylate were prepared according to Table 1. A 2% wt. fraction of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as photoinitiator was used in all resins. The resins were SLA printed into tiles about 1 cm×about 1 cm×about 0.2 cm in size using a Peopoly Moai SLA 3D printer with a about 210 mW laser and laser setting of about 75. Once printed, the tiles were removed from the build plate and washed in ethanol. The resins were also drop casted onto glass slides, UV-cured using a Dymax Light Curing System (Model 5000 Flood) and washed with ethanol. The contact angles of the 3D printed tiles and the UV-cured films were measured using a 5 μL drop of water.

TABLE 1 Formulations of resins used to prepare tiles and films in Example 15. % wt. % wt. ethyl % wt. 2- % wt. 1H,1H- trimethylol- (2,4,6- ethylhexyl- PERFLUOROOCTYL propane trimethylbenzoyl) acrylate METHACRYLATE triacrylate phenylphosphinate 0 0 98 2 1 1 96 2 5 5 88 2 10 10 78 2 20 20 58 2 30 30 38 2 40 40 18 2

Printing, Sintering and Characterization:

Ink Characterization:

TGA analysis of resin and functional material resins were performed via a TGA A588 TGA-IR module.

SLA printing of 3D products: 3D products using functional material (silver salt, silver and graphene) were printed using Peopoly Moai Laser SLA 3D Printer (Technical Specifications: Build Volume: 130×130×180 mm, Laser spot size: about 70 microns, Laser wave length: about 405 nm, Laser power: about 150 mW, Machine size: 330×340×660 mm, Layer Height: about 10 to about 200 microns, Z resolution: Layer Height: about 10 to about 200 m). Products were printed using non-stick liner coated vat with laser power 58 and XY speed set 4.

Sintering of printed 3D products: 3D products were thermally sintered at about 200 to about 250° C. temperature (program) ranges by varying time using reflow oven under nitrogen with about 500 ppm oxygen. Intense pulsed light sintering (photonic curing) was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm2 for about 3000 s under ambient conditions.

Characterization of 3D products: A two-point probe method was used to measure the resistance of the 3D printed products using a multimeter after thermal and photonic sintering. Scanning electron microscopy (SEM) images were acquired with a Hitachi SU3500.

A summary of the exemplary formulations, their processing and the resulting 3D printed product is provided in Table 2 below.

TABLE 2 Summary of Examples 1-15 and resulting in 3D printed products. All examples were made using commercially available resins, except for Examples 8, 9 and 15 where resin components were specifically selected and prepared. Example Functional No. component Resin Processing Comment 1 (comparative silver Acrylate-based 1) SLA printing Non- example) neodecanoate + resin of resin, conducting 2-ethyl-2- (FSL 3D) 2) coating of products oxazoline functional (7% Ag metal) component 3) thermal sintering 2 Functional silver Acrylate-based 1) SLA printing Non- Coating neodecanoate + resin 2) thermal Conducting 2-ethyl-2- (FSL 3D) sintering products oxazoline (1.97% Ag metal) 3 Functional silver Acrylate-based 1) SLA printing Non- Coating neodecanoate + resin 2) thermal Conducting 2-ethyl-2- (FSL 3D) sintering products oxazoline (3.94% Ag metal) 4 Functional silver Acrylate-based 1) SLA printing Conducting Coating neodecanoate + resin 2) thermal products 2-ethyl-2- (FSL 3D) sintering ~20-50 Ω/cm oxazoline (7% Ag metal) 5 Functional silver Acrylate-based 1) SLA printing Conducting Coating neodecanoate + resin 2) thermal products 2-ethyl-2- (FSL 3D) sintering ~10-25 Ω/cm oxazoline (7.9% Ag metal) 6 Functional silver Acrylate-based 1) SLA printing Conducting Coating neodecanoate + resin 2) thermal products 2-ethyl-2- (FSL 3D) sintering ~18-23 Ω/cm oxazoline (9.85% Ag metal) 7 Functional silver Acrylate-based 1) SLA printing Non- Coating neodecanoate resin 2) thermal conducting (7% Ag metal) (FSL 3D) sintering products 8 Functional silver 10% 1) SLA printing Conducting Coating neodacanoate + trimethylolpropane 2) thermal products 2-ethyl-2- triacrylate sintering oxazoline (TMPTA), 89% 2- (7.9% Ag metal) ethylhexylacrylate, 1% ethyl (2,4,6- trimethylbenzoyl) phenylphosphinate (TPO-L) 9 Composite silver 99% TMPTA, 1) SLA printing Non- neodacanoate + 1% TPO-L 2) thermal conducting 2-ethyl-2- sintering products oxazoline (7.9% Ag metal) 10 silver nitrate + Acrylate-based 1) SLA printing Non- Graded 2-ethyl-2- resin 2) thermal conducting Composition oxazoline (FSL 3D) sintering products (7% Ag metal) 11 silver acetate + Acrylate-based 1) SLA printing Non- Graded 2-ethyl-2- resin 2) thermal conducting Composition oxazoline (FSL 3D) sintering products (7% Ag metal) 12 copper formate + Acrylate-based 1) SLA printing Non- Graded aminodiol resin 2) thermal conducting Composition (7% Cu metal) (FSL 3D) sintering products 13 graphene Acrylate-based 1) SLA printing Non- Functional (GRN235) + resin 2) thermal Conducting Coating dispersing agent (FSL 3D) sintering products (BYK 180) (0.05% graphene in total ink 14 graphene Acrylate-based 1) SLA printing Conducting Functional (GRN235) + resin 2) thermal products Coating dispersing agent (FSL 3D) sintering ~1-5 KΩ/cm (BYK 180) (0.4% graphene in total ink 15 Various % of Acrylate-based 1) SLA printing Non- Functional 1H,1H- resin 2) UV conducting Coating perfluorooctyl (See Example sintering products methacrylate 15) (hydrophobic properties)

Additional Analysis

Examples of 3D printed products are shown in FIGS. 2A, 2B, and 2C.

SEM images of 3D printed cylinders of Example 4 are shown in FIGS. 3A-3C. The cylinders were about 1 cm in length and diameters of a) about 350 mm, b) about 500 mm and c) about 1500 mm. The images of the cross-sections were taken near the surface of the cylinder to demonstrate the phase separation of silver and polymer. The silver appears as the bright areas and the polymer as the dark areas. As the volume of the 3D printed product increases (increasing diameter of cylinder), the thickness of the functional coating increases. The schematic in FIG. 3D provides a perspective of where the SEM images where taken on the cylinders (red circle, top left at the interface of the surface layer and rest of the product).

Concentration gradient in 3D printed product of Example 4. Cross-sectional SEM images of the interface of a 3D printed product are shown in FIGS. 4A and 4B. The images show a top layer of silver formed on the polymer core. Within the polymer core, a concentration gradient of silver nanoparticles was observed, with the concentration of silver (bright areas) decreasing with distance away from the surface of the product.

Resistance of 1 cm cylinders of Examples 5 and 6 (Tables 3 and 4). Conductivity of silver cylinders (silver thickness of from about 200 to about 500 nm) under various conditions—increasing Ag content (Table 3) and decreasing cylinder diameter (Table 4).

TABLE 3 Sintering conditions Resistance of 1 cm × 1500 mm rod (W) Silver content 7.88% Ag 9.85% Ag 250° C./30 mins 56 22.5 Photo (stage 40)/250° C._30 182 19 min & 350 V/1500 μs_1X

Increasing the silver content in the resin decreased the cylinder resistance.

TABLE 4 Resistance of 1 cm rod (Ω) Diameter of rod (μm) Summary of 7.88% 1500 1000 750 250° C./30 mins 56 22 38 250° C./60 mins 27 12 14 200° C./60 mins 147 112 80

Decreasing cylinder diameter led to improved resistance.

TGA of AgResin_7.88% Ag SLA 3D Product Cured in Air of Example 5

The residual mass of the SLA 3D product was about 9.66% while the initial formulation predicted a residual mass of about 7.88% (silver content) (FIG. 5 ).

Formulation of Silver Neodecanoate 3D Printable Resins:

As outlined above in the many examples, for SLA 3D printing, the molecular silver ink formulations were prepared by first dissolving silver salt in an amine. Subsequently, commercial acrylate-based resin (Pegasus, FSL3D) or flexible resin (photocentric 3D) was added in to the silver/amine complex to form the final formulation with about 2 to about 10 wt % silver content based on the total weight of the formulation (see Table 5 below).

TABLE 5 Ag 2-Ethyl-2- Ag Resin Neodecanoate oxazoline Resin Total 1.97% Ag 6.25 g 1.38 ml 114.99 122.62 3.84% Ag 12.5 g 2.76 ml 107.36 122.62 7.88% Ag 25.0 g 5.52 ml 92.1 g 122.62 9.85% Ag 31.25 g 6.9 ml 84.47 g 122.62

Optical images of 3D printed cylinders of Example 15 are shown in FIGS. 6A and 6B.

FIG. 6B shows the increase in the contact angle of the tiles with the addition of a fluorinated monomer to the resin, relative to the contact angles shown in FIG. 6A. FIG. 7 shows that using the same resin, SLA printed tiles generate surfaces with higher contact angles than those UV-cured as a film.

Formulation Examples 16-53

Based on the observed product results and morphologies arising from Examples 1-15, Examples 16-57 provide additional embodiments of formulations and printing conditions which resulted in functional coatings, graded compositions, and composites.

Formulating Considerations for Functional Components and Resins

In these examples, the 3D printing SLA resins have three components: mono-functional monomers, di-, tri- and tetra-functional cross-linking agents and a photoinitiator. Various cross-linking agents composed of different reactive end groups and inner subunits were tested. Higher cross-linking percentage led to the prints having greater tensile strength with graded and composite structure products, and lower cross-linking percentages usually having lower resistivities with functionally coated phase separated products.

To design functional products, and tune the chemical and/or physical properties, the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components were leveraged to control the placement of functional components. In certain examples, when components had similar hydrophilic or hydrophobic properties, the components had less of a driving force to phase separate upon polymerization. When the components differed in their hydrophobicity or hydrophilicity, the functional component had a larger driving force to separate from the composition (e.g. polymerizing monomer/cross-linking agent mixture).

There are commercial resins available with the capability of creating successful multi-material print structures. When more design flexibility is needed to create complex structures, resins were provided in the present disclosure that can be chemically altered and still remain stable for application. In some examples, the resin formulations shown in the Tables (e.g. Tables 2, 6 and 7) provided useful products without the listed functional components. In these instances, the resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.

Example 16: Ag Precursor+(15% EGDA, 84% EHA) Resin

About 1.5 g of ethyleneglycol diacrylate, about 8.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 17: Ag Precursor+(20% EGDA, 79% EHA) Resin

About 2.0 g of ethyleneglycol diacrylate, about 7.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 18: Ag Precursor+(25% EGDA, 74% EHA) Resin

About 2.5 g of ethyleneglycol diacrylate, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 19: Ag Precursor+(35% EGDA, 64% EHA) Resin

About 3.5 g of ethyleneglycol diacrylate, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 20: Ag Precursor+(50% EGDA, 49% EHA) Resin

About 5.0 g of ethyleneglycol diacrylate, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 21: Ag Precursor+(15% PEGDA250, 84% EHA) Resin

About 1.5 g of polyethyleneglycol diacrylate Mn 250, about 8.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 22: Ag Precursor+(20% PEGDA250, 79% EHA) Resin

About 2.0 g of polyethyleneglycol diacrylate Mn 250, about 7.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 23: Ag Precursor+(25% PEGDA250, 74% EHA) Resin

About 2.5 g of polyethyleneglycol diacrylate Mn 250, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 24: Ag Precursor+(35% PEGDA250, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 25: Ag Precursor+(50% PEGDA250, 49% EHA) Resin

About 5.0 g of polyethyleneglycol diacrylate Mn 250, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 26: Ag Precursor+(99% PEGDA250) Resin

About 9.9 g of polyethyleneglycol diacrylate Mn 250 and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 1 minute. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 27: Ag Precursor+(25% TEGDA, 74% EHA) Resin

About 2.5 g of tetraethyleneglycol diacrylate, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 28: Ag Precursor+(35% TEGDA, 64% EHA) Resin

About 3.5 g of tetraethyleneglycol diacrylate, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 29: Ag Precursor+(50% TEGDA, 49% EHA) Resin

About 5.0 g of tetraethyleneglycol diacrylate, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 30: Ag Precursor+(99% TEGDA) Resin

About 9.9 g of tetraethyleneglycol diacrylate and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 1 minute. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 31: Ag Precursor+(25% PEGDA575, 74% EHA) Resin

About 2.5 g of polyethyleneglycol diacrylate Mn 575, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 32: Ag Precursor+(35% PEGDA575, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 33: Ag Precursor+(45% PEGDA575, 54% EHA) Resin

About 4.5 g of polyethyleneglycol diacrylate Mn 575, about 5.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 34: Ag Precursor+(50% PEGDA575, 49% EHA) Resin

About 5.0 g of polyethyleneglycol diacrylate Mn 575, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 35: Ag Precursor+(65% PEGDA575, 34% EHA) Resin

About 6.5 g of polyethyleneglycol diacrylate Mn 575, about 3.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 36: Ag Precursor+(25% PEGDA700, 74% EHA) Resin

About 2.5 g of polyethyleneglycol diacrylate Mn 700, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 37: Ag Precursor+(35% PEGDA700, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 700, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 38: Ag Precursor+(50% PEGDA700, 49% EHA) Resin

About 5.0 g of polyethyleneglycol diacrylate Mn 700, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 39: Ag Precursor+(60% PEGDA700, 39% EHA) Resin

About 6.0 g of polyethyleneglycol diacrylate Mn 700, about 3.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 40: Ag Precursor+(80% PEGDA700, 19% EHA) Resin

About 8.0 g of polyethyleneglycol diacrylate Mn 700, about 1.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for 2 minutes at 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 41: Ag Precursor+(99% PEGDA700) Resin

About 9.9 g of polyethyleneglycol diacrylate Mn 700 and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 42: Ag Precursor+(35% 1,4-butanediol diacrylate, 64% EHA) Resin

About 3.5 g of 1,4-butanediol diacrylate, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 43: Ag Precursor+(50% 1,4-Butanediol Diacrylate, 4.9% EHA) Resin

About 5.0 g of 1,4-butanediol diacrylate, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 44: Ag Precursor+(65% 1,4-Butanediol Diacrylate, 34% EHA) Resin

About 6.5 g of 1,4-butanediol diacrylate, about 3.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 45: Ag Precursor+(35% 1,6-Hexanediol Diacrylate, 64% EHA) Resin

About 3.5 g of 1,6-hexanediol diacrylate, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 46: Ag Precursor+(50% 1,6-Hexanediol Diacrylate, 4.9% EHA) Resin

About 5.0 g of 1,6-hexanediol diacrylate, about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 47: Ag Precursor+(65% 1,6-Hexanediol Diacrylate, 34% EHA) Resin

About 6.5 g of 1,6-hexanediol diacrylate, about 3.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 48: Ag Precursor+(50% 1,6-Hexanediol Diacrylate, 49% EGMEA) Resin

About 5.0 g of 1,6-hexanediol diacrylate, about 4.9 g of ethyleneglycol methyl ether acrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 49: Ag Precursor+(25% DTMPTA, 74% EHA) Resin

About 2.5 g of di(trimethylolpropane) tetraacrylate, about 7.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 50: TiO₂+(35% PEGDA250, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. To this vial, about 0.25 g of TiO₂ functionalized with 2-methoxy(polyethyleneoxy)propyl trimethoxysilane were added and the combined mixture was then sonicated overnight in the dark. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 51: TiO₂+(35% PEGDA250, 64% EHA and Toluene) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.17 g of 2-ethylhexylacrylate, about 2.3 ml toluene and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. To this vial, about 0.25 g of TiO₂ functionalized with 2-methoxy(polyethyleneoxy)propyl trimethoxysilane were added and the combined mixture was then sonicated overnight in the dark. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

FIG. 17 shows SEM images of 3D TiO₂ products printed without toluene (a, b and c) and with toluene (d, e and f) and FIG. 18 shows wt % of TiO₂ as a function of distance from the surface of the 3D TiO₂ products. Products without toluene had a wider TiO₂ wt % distribution.

Example 52: Barium Strontium Titanate (BST)+(35% PEGDA250, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. To this vial, about 0.25 g of Barium Strontium Titanate (BST) functionalized with 2-methoxy(polyethyleneoxy)propyl trimethoxysilane were added and the combined mixture was then sonicated overnight in the dark. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

FIG. 19 shows SEM images of 3D Barium Strontium Titanate (BST) product.

Example 53: Iron Oxide+(35% PEGDA250, 64% EHA) Resin

About 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. To this vial, about 0.25 g of iron oxide were added and the combined mixture was then sonicated overnight in the dark. The resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

FIG. 20 shows a) SEM images of the cross-section of a printed cylinder with iron oxide nanoparticles. The nanoparticles appear as bright areas in the SEM; Energy dispersion spectroscopy (EDS) analysis of the SEM mapping out b) carbon and c) iron in the sample.

The results of testing the formulations described above in 3D printing processes are summarized below in Tables 6-8.

TABLE 6 Summary of Examples of 3D printing products that generate functional coatings defined by the concentrations of about 15% to about 35% mol difunctional cross-linking agent of the resin mixture. % mol cross- Example Functional linking No. component Resin agent Processing Comment 16 AgND + EtOxa 15% wt. EGDA, 16 1) SLA printing Conducting (7.9% Ag metal) 84% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 0.64 Ω/cm 17 AgND + EtOxa 20% wt. EGDA, 21 1) SLA printing Conducting (7.9% Ag metal) 79% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 0.88 Ω/cm 18 AgND + EtOxa 25% wt. EGDA, 27 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1 Ω/cm 21 AgND + EtOxa 15% wt. PEGDA250, 11 1) SLA printing Conducting (7.9% Ag metal) 84% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.3 Ω/cm 22 AgND + EtOxa 20% wt. PEGDA250, 14 1) SLA printing Conducting (7.9% Ag metal) 79% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1.36 Ω/cm 23 AgND + EtOxa 25% wt. PEGDA250, 20 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2 Ω/cm 24 AgND + EtOxa 35% wt. PEGDA250, 29 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt TPO-L sintering 1.4 Ω/cm 27 AgND + EtOxa 25% wt. TEGDA, 18 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1.85 Ω/cm 28 AgND + EtOxa 35% wt. TEGDA, 26 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1.28 Ω/cm 31 AgND + EtOxa 25% wt. PEGDA575, 12 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.96 Ω/cm 32 AgND + EtOxa 35% wt. PEGDA575, 20 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.16 Ω/cm 33 AgND + EtOxa 45% wt. PEGDA575, 28 1) SLA printing Conducting (7.9% Ag metal) 54% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.24 Ω/cm 34 AgND + EtOxa 50% wt. PEGDA575, 33 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 7.42 Ω/cm 36 AgND + EtOxa 25% wt. PEG700, 11 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.23 Ω/cm 37 AgND + EtOxa 35% wt. PEGDA700, 18 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.64 Ω/cm 42 AgND + EtOxa 35% wt. BDDA, 33 1) SLA Conducting (7.9% Ag metal) 64% wt. EHA, printing products 1% TPO-L 2) thermal 1.32 Ω/cm sintering 45 AgND + EtOxa 35% wt. HDDA, 31 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 0.94 Ω/cm 50 2.5% TiO₂ functionalized 35% wt. PEGDA250, 29 1) SLA printing Functional with 2- 64% wt. EHA, 2) thermal products methoxy(polyethyleneoxy)propyl 1% wt. TPO-L sintering with phase trimethoxysilane separation (e.g. coated) 51 2.5% TiO₂ functionalized 35% wt. PEGDA250, 29 1) SLA printing Functional with 2- 61.7% wt. EHA, 2) thermal products methoxy(polyethyleneoxy)propyl 1% wt. TPO-L, sintering with phase trimethoxysilane toluene separation 52 2.5% Barium Strontium 35% wt. PEGDA250, 29 1) SLA printing Functional Titanate (BST) 64% wt. EHA, 2) thermal products functionalized with 2- 1% wt. TPO-L sintering with phase methoxy(polyethyleneoxy)propyl separation trimethoxysilane 53 2.5% Iron oxide 35% wt. PEGDA250, 29 1) SLA printing Functional 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering with phase separation

TABLE 7 Summary of Examples of 3D printing products that generate products with functionally graded compositions defined by the concentrations of about 35% to about 80% mol difunctional cross-linking agent of the resin mixture or about 10% to about 50% mol tetrafunctional cross-linking agent of the resin mixture. % mol cross- Example Functional linking No. component Resin agent Processing Comment 19 AgND + EtOxa 35% wt. EGDA, 37 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 37 Ω/cm 20 AgND + EtOxa 50% wt. EGDA, 52 1) SLA printing Non- (7.9% Ag metal) 49% wt. EHA, 2) thermal Conducting 1% wt. TPO-L sintering products 25 AgND + EtOxa 50% wt. PEGDA250, 43 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 7.6 Ω/cm 29 AgND + EtOxa 50% wt. TEGDA, 40 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 13.16 Ω/cm 35 AgND + EtOxa 65% wt. PEGDA575, 50 1) SLA printing Conducting (7.9% Ag metal) 34% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 21.04 Ω/cm 38 AgND + EtOxa 50% wt. PEGDA700, 32 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 12.55 Ω/cm 39 AgND + EtOxa 60% wt. PEGDA700, 42 1) SLA printing Conducting (7.9% Ag metal) 39% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 28.44 Ω/cm 40 AgND + EtOxa 80% wt. PEGDA700, 68 1) SLA printing Conducting (7.9% Ag metal) 19% wt. EHA, 2) thermal products 1% TPO-L sintering 25.94 Ω/cm 43 AgND + EtOxa 50% wt. BDDA, 48 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 7.24 Ω/cm 44 AgND + EtOxa 65% wt. BDDA, 69 1) SLA printing Conducting (7.9% Ag metal) 34% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 100-500 Ω/cm 46 AgND + EtOxa 50% wt. HDDA, 45 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.9 Ω/cm 47 AgND + EtOxa 65% wt. HDDA, 65 1) SLA printing Conducting (7.9% Ag metal) 34% wt. EHA, 2) thermal products 1% TPO-L sintering 37.4 Ω/cm 48 AgND + EtOxa 50% wt. HDDA, 50 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EGMEA, 2) thermal products 1% wt. TPO-L sintering 112 Ω/cm 49 AgND + EtOxa 25% wt. DTMPTA, 16 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering KΩ/cm

TABLE 8 Summary of Examples of 3D printing products that generate products with composites as defined by the concentrations of about 80% to about 99% mol difunctional cross-linking agent of the resin mixture. % mol cross- Example Functional linking No. component Resin agent Processing Comment 26 AgND + EtOxa 99% wt. PEGDA250, 99 1) SLA printing Non- (7.9% Ag metal) 1% wt. TPO-L 2) thermal Conducting sintering products 30 AgND + EtOxa 99% wt. TEGDA, 99 1) SLA printing Non- (7.9% Ag metal) 1% wt. TPO-L 2) thermal Conducting sintering products 41 AgND + EtOxa 99% wt. PEGDA700, 98 1) SLA printing Non- (7.9% Ag metal) 1% wt. TPO-L 2) thermal conducting sintering products

Formulations Generating Coatings Vs Functionally Graded Compositions.

When 3D printing resins have multiple components, the morphology of the printed product may depend on the concentration of cross-linking agent.

With reference to the Examples 16-53, changes in morphology as a function of cross-linking agent concentrations for resins containing non-polymerizing functional and/or functional precursor components were observed. Where the non-polymerizing functional precursor component was silver neodecanoate, it may be converted to silver post printing by heating to elevated temperatures. Other examples include non-polymerizing functional nanoparticles, such as TiO₂, F₂O₃ and ZnO.

3D Printing of Polymer-Silver Structures.

Using a difunctional cross-linking agent (e.g. EGDA, PEGDA250, PEGDA575 and PEGDA700), various morphologies in the printed product may be formed depending on the concentration of cross-linking agent. FIG. 8 shows the amount of silver (% wt) at the surface decreased with increased concentration of cross-linking agent. The concentration of silver at the surface can determine the resistance value of the printed product. As the concentration of cross-linking agent increases, the resistance of the silver coating increases due to the lower concentration of silver at the surface (FIG. 9 ). FIG. 10 illustrates the change in the concentration of silver in a 3D printed cylinder depending on the amount of EGDA cross-linking agent.

Example 54: 3D Printed Strain Sensors

A resin consisting of about 50% PEGDA575, about 49% EHA was prepared by mixing about 5.0 g of polyethyleneglycol diacrylate (Mn 575), about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. The resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Next, a resin consisting of about 35% PEGDA250, about 64% EHA was prepared by mixing about 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. The resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

The final resin composition was prepared by mixing about 2.5 g of silver neodecanoate dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixed resin (about 7.5 ml (about 50% PEGDA575, about 49% EHA)+about 2.5 ml (about 35% PEGDA250, about 64% EHA)). The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into 3D truss products and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Example 55: 3D Printed Products with Multimaterial Resin of Silver Precursor, Graphene and Acrylate Resin (7.88% Ag+0.2% Graphene Products Using Mixed Resin (7.5 ml (50% PEGDA575, 49% EHA)+2.5 ml (35% PEGDA250, 64% EHA))

About 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 0.245 g of graphene and about 9.18 g of the acrylate mixed resin (about 7.5 ml (about 50% PEGDA575, about 49% EHA)+about 2.5 ml (about 35% PEGDA250, about 64% EHA)). The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm and sonicated for about 15 mins. The resin was SLA printed into 3D truss products and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Conducting structures: ˜5-10 Ω/cm resistance, silver is phase separated (e.g. coated)

Example 56: 3D Printed Products with Multimaterial Resin of Silver Precursor, Graphene, Barium Strontium Titanate and Acrylate Resin (7.88% Ag+0.2% Graphene+0.5% BST Products Using Mixed Resin (7.5 ml (50% PEGDA575, 49% EHA)+2.5 ml (35% PEGDA250, 64% EHA))

About 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 0.245 g of graphene, about 0.0613 g of functionalised barium strontium titanate (BST) and about 9.12 g of the acrylate mixed resin (about 7.5 ml (about 50% PEGDA575, about 49% EHA)+about 2.5 ml (about 35% PEGDA250, about 64% EHA)). The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm and sonicated for about 15 mins. The resin was SLA printed into 3D truss products and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

Conducting structures: ˜5-10 Ω/cm resistance, silver is phase separated

Graded Silver as Strain Sensors

For samples made with an intermediate concentration of difunctional cross-linking agent (about 35% to about 80% mol), the products formed a graded composition with a high concentration of silver particles in the polymer near the surface of the product and decreasing in concentration away from the surface of the product. The morphology of silver particles made it possible to generate a strain sensor as described in FIG. 11 . As the product was compressed, the silver nanoparticles embedded in the product make contact increasing the electrical conductivity of the sample as shown in FIG. 12 .

Example 57: Evaluation of the Antibacterial Behaviors of 3D Printed Ag Product and the Control Resin Product without Ag Through Halo Inhibition Zone Tests

Silver has been known to possess a broad-spectrum against bacteria and limited toxicity towards mammalian cells. Nano-silver particles of which antibacterial and antifungal properties have been shown in various in vitro and in vivo studies are used in many medical and dental fields for the prevention of infection. Currently, nano-silver particles have been applied to a wide range of health-care products, such as burn dressings, water purification systems, and dental and medical devices. For example silver incorporated in orthodontic brackets will be useful in dentistry. 3D printed functional products of this kind can be produced according to the formulations and methods of the present disclosure.

Control Product: (about 35% PEGDA575, about 64% EHA) Resin: about 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. The resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

About 0.5% Ag Products: Ag Precursor+(about 35% PEGDA575, about 64% EHA) Resin: about 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 0.158 g of silver neodecanoate were dissolved in about 0.035 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 12.08 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed and then thermally sintered at 250° C. temperature (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

About 1.0% Ag Products: Ag Precursor+(about 35% PEGDA575, about 64% EHA) Resin: about 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. In a separate vial, about 0.317 g of silver neodecanoate were dissolved in about 0.070 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 11.88 g of the acrylate mixture from the first vial. The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.

The procedure used to conduct the antimicrobial tests and obtain the results shown in FIGS. 13-16 are described in Balouiri et al. Journal of Pharmaceutical Analysis 6 (2016) 71-79 and Belkhair et al. RSC Adv., 2015, 5, 40932-40939, both of which are herein incorporated by reference in their entirety. As shown in FIGS. 13 , there is bacterial growth inhibition in the Ag products compared to controls that do not contain Ag in the zones that arise in proximity to scaffolds. FIG. 13 shows evaluation of the antibacterial behaviors of a 3D printed Ag object and a control resin object without Ag through halo inhibition zone tests on E. coli plated agar plates. In the proximity of the 3D objects with Ag, growth is inhibited due to Ag leaching. FIG. 14 shows bacterial growth on the 3D object with and without Ag in culture. FIG. 15 shows bacterial growth kinetics with the 3D object with and without Ag in a liquid culture. FIG. 16 shows bacterial growth kinetics of the supernatant from the FIG. 15 study in liquid culture without 3D objects. In all examples, the Ag object shows bacterial growth inhibition as reflected by the lower absorbance values. In FIG. 15 , the control provided the highest absorbance readings over time.

Example 58: SLA Printing of Hydrophobic Tiles Using Fluorinated Monomers

Molecular coatings can be generated from slow polymerizing monomers (methacrylates) in a resin containing mostly fast polymerizing acrylates. In one embodiment, fluorinated methacrylates were used to make a fluorinated hydrophobic coating from a resin containing primarily non-fluorinated acrylates. The resulting products are useful for anti-fouling/anti-microbial and de-icing applications.

Three series of resins containing varying concentrations of fluorinated monomer, 2-ethylhexyl acrylate and trimethylolpropane triacrylate were prepared according to Tables 9, 10 and 11. Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate was used as a photoinitiator in all resins. The resins were SLA printed into tiles 1 cm×1 cm×0.2 cm in size using a Peopoly Moai SLA 3D printer with a about 210 mW laser and laser setting of about 75. Once printed, the tiles were removed from the build plate and washed in ethanol. The contact angles of the 3D printed tiles and the UV-cured films were measured using a 5 μL drop of water.

TABLE 9 Resin formulations using 1H,1H-perfluorooctyl methacrylate. % wt. 2- % wt. 1H,1H- % wt. % wt. ethyl (2,4,6- ethylhexyl- PERFLUOROOCTYL trimethylolpropane trimethylbenzoyl) acrylate METHACRYLATE triacrylate phenylphosphinate 0 0 98 2 1 1 96 2 5 5 88 2 10 10 78 2 20 20 58 2 30 30 38 2 40 40 18 2

TABLE 10 Resin formulations using 2,2,3,4,4,4-hexafluorobutyl acrylate. % wt. 2,2,3,4,4,4- % wt. % wt. ethyl (2,4,6- HEXAFLUOROBUTYL trimethylolpropane trimethylbenzoyl) ACRYLATE triacrylate phenylphosphinate 1.0 98.0 1.0 5.0 94.0 1.0 10.0 89.0 1.0 20.0 79.0 1.0 30.0 69.0 1.0 40.0 59.0 1.0

TABLE 11 Resin formulations using 2,2,3,4,4,4-hexafluorobutyl methacrylate. % wt. 2,2,3,4,4,4- % wt. % wt. ethyl (2,4,6- HEXAFLUOROBUTYL trimethylolpropane trimethylbenzoyl) METHACRYLATE triacrylate phenylphosphinate 1.0 98.0 1.0 5.0 94.0 1.0 10.0 89.0 1.0 20.0 79.0 1.0 30.0 69.0 1.0

The results in FIG. 21 are the contact angles of tiles printed from the photoresins containing a fluorinated monomer of varying concentrations. The results show that as the weight fraction of fluorinated monomer increases, the contact angles of the surfaces of the tiles increases. The photoresins with fluorinated methacrylates (i.e. 1H, 1H-perfluorooctyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl methacrylate) have greater contact angles at lower concentrations of % wt. fluorinated monomer in comparison to the fluorinated acrylate (i.e. 2,2,3,4,4,4-hexafluorobutyl acrylate). Without being bound by theory, this result may be due to the lower polymerization rates of methacrylates in comparison to acrylates that cause these monomers to polymerize at later stages during the printing process and cause these monomers to concentrate at the surface of the product.

FIG. 22 illustrates the changes in contact angles as layers of polymers are removed for a tile printed using about 20% wt. 2,2,3,4,4,4-hexafluorobutyl methacrylate. The results show that the contact angle of the tile decreased as a function of the depth of the tile, an indication that the fluorinated component was concentrated at the surface of the tile.

Example 59: SLA Printing of Products—Infiltration of One Photopolymer

To a 20 mL scintillation vial, about 4.9 g of ethylene glycol phenyl ether acrylate and about 4.9 g of 1,6-hexanediol diacrylate were added. To the mixture, about 0.2 g (2% wt) photoinitiator, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), was added. The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. The resin was used to print a custom designed structure of platelets separated by spaces and held together with support bridges using a stereolithographic printer (FIG. 26 a ). The dimensions of the spaces and support bridges varied depending on resolution of the photopolymer and SLA printer. Once printed, the structure was sonicated three times in isopropanol for about 10 min to remove excess resin from the spaces in between and surrounding the structure and then dried. The structure was UV cured for about 5 min in a second stage to ensure complete polymerization. In a separate 20 mL scintillation vial, the second set of thermal or UV curable monomer(s)/crosslinker(s) were weighed at appropriate ratios to be cured (about 2.5 g of epoxypropoxypropyl terminated polydimtheylsiloxane and about 2.5 g of aminopropyl terminated polydimethylsiloxane). This was mixed by manually mixing or using a vortex mixer for about 30 s. The spaces in the 3D printed structure were filled by either submerging the structure in the second set of monomer(s)/crosslinker(s) mixture or by capillary action and then thermally cured at about 160° C. for about 2 hours.

Example 59a: SLA Printing of Products—Infiltration of One Photopolymer

To a 500 mL disposable container, about 98.5 g of poly(ethylene glycol) diacrylate Mn 250; 1.3 g (1.3 wt %) photoinitiator, 2,4,6-trimethylbenzoyldi-phenylphosphinate (TPO-L); and 0.2 g (0.2 wt %) UV absorber, 2-nitrophenyl phenyl sulfide (NPS), was added. The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. The resin was used to print a custom designed structure of platelets separated by spaces and held together with support bridges using a stereolithographic printer (FIG. 27 a ). Once printed, the structure was sonicated three times in isopropanol for about 10 min to remove excess resin from the spaces in between and surrounding the structure and then dried. In a separate 20 mL scintillation vial, the second set of thermal curable resin was mixed, containing 5.0 g of epoxypropoxypropyl terminated polydimtheylsiloxane and 5.0 g of aminopropyl terminated polydimethylsiloxane. This was mixed by using a vortex mixer for about 30 s. The spaces in the 3D printed structure were filled by submerging the structure in the second set of monomer(s)/crosslinker(s) mixture and then thermally cured at about 160° C. for about 2.5 hours. The results can be found in FIG. 30 , where a-d) show top and e-f) show side images of the custom designed structure of platelets separated by spaces and held together with support bridges using a stereolithographic printer. a, c, and e) show the structure after printing and before infiltration with the thermal curable resin. b, d, f) show the structure after infiltration and thermal curing of the second resin.

Examples 60a-60b: SLA Printing of Products—Phase Separation with One Photopolymer and a First Component (e.g. Functional Material)

Example 60a: The commercial Form Labs Ceramic resin (FLCEWH01, Formlabs, contains acrylated monomers, photoinitiator(s), <1 wt % additives, silica filler) was shaken for about 1 min, which includes a photoinitiator and functional material. The homogeneous mixture was used to produce a similar 3D printed structure as above for the Infiltration of One Photopolymer method. The structure was washed three times in isopropanol to remove residual resin, then UV cured for about 5 min to ensure complete polymerization. The preliminary results can be found in FIG. 26 .

Example 60b: The First Set of Photopolymerizing Monomer(s)/Crosslinker(s)/Functional

material(s) contains about a 1:1 weight ratio of ethylene glycol phenyl ether acrylate and 1,6-hexanediol diacrylate, which was weighed in a 20 mL scintillation vial (4.9 g of each monomer and crosslinker). To the mixture, about 2 wt % diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, about 0.2 g)) was added as the photoinitiator. The functional material, hydride terminated polydimethylsiloxane, about 7 to about 10 cSt, was then added at about 10 wt % of the entire resin mixture (about 9:1 weight ratio of first set to functional material). The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s so that some of the polydimethylsiloxane dissolves in the monomer resin with the mixing. The structure was immediately UV cured after printing for about 5 min to ensure complete polymerization. The preliminary results can be found in FIGS. 27-29 and Table 12.

TABLE 12 Energy dispersive X-ray spectroscopy (EDS) Spectrum of Cross-Section of Structure from FIG. 29 Showing Variability in Si Across the Platelets and Spaces. Spectrum # Wt % C Wt % O Wt % Si 1 66.79 31.43 1.79 2 68.61 30.43 0.93 3 59.53 37.33 3.14 4 63.70 34.33 1.98 5 73.24 26.39 0.37 6 73.46 25.72 0.82 7 72.24 26.82 0.93 8 64.75 33.07 2.17 9 66.89 31.42 1.68 10 65.31 33.40 1.29

Example 61: SLA Printing of Products—Phase Separation with One Photopolymer and a Thermal Curable Polymer

The first set of faster photopolymerizing monomer(s)/crosslinker(s)/functional material(s) is added in a weight ratio for the optimal chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties in a 20 mL scintillation vial. To the mixture, about 0.5 to about 3 weight percent photoinitiator is added. The second set of monomer(s)/crosslinker(s)/functional material(s) with different thermodynamic miscibility and/or an orthogonal polymerization mechanism (thermal curable monomer(s)/crosslinker(s)/functional material(s)) are weighed out in a 20 mL scintillation vial in appropriate ratios for the desired chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties. The two resin sets are added together in the appropriate ratio for phase separation and desired physical properties. The mixture is dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. Phase separation of the second polymer resin into the spaces in between or confined within the first polymer printed structure may occur due to different thermodynamic miscibilities (e.g. monomers are polar vs. non-polar, aromatic vs. aliphatic, aliphatic vs. polydimethylsiloxane-functionalized). The final structure is thermally cured using a reflow oven (to polymerize the second polymerizable component) followed by UV curing for about 5 min to ensure complete polymerization.

Example 62: SLA Printing of Products—Phase Separation with Two Photopolymers

The first set of faster photopolymerizing monomer(s)/crosslinker(s)/functional material(s) is added in a weight ratio for the optimal chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties in a 20 mL scintillation vial. To the mixture, about 0.5 to about 3 weight percent photoinitiator is added. The second set of monomer(s)/crosslinker(s)/functional material(s) with slower kinetics or different thermodynamic miscibility and/or an orthogonal polymerization mechanism were weighed out in a 20 mL scintillation vial in appropriate ratios for the desired chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties. In addition, a second photoinitiator, that initiates an orthogonal polymerization mechanism to the first set, may be added at about 0.5 to about 3 weight percent of the second set resin. The two resin sets are added together in the appropriate ratio for phase separation and desired physical properties. The mixture is dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. Phase separation of the second polymer resin into the spaces in between the first polymer printed structure may occur due to kinetics (slower photopolymerization) and/or different thermodynamic miscibilities (e.g. monomers are polar vs. non-polar, aromatic vs. aliphatic, aliphatic vs. polydimethylsiloxane-functionalized). The final structure is washed three times in isopropanol by sonicating for about 10 min to remove residual resin, then UV cured for about 5 min to ensure complete polymerization.

Example 62a: SLA Printing of Products—Phase Separation with Two Photopolymers

The first set of faster photopolymerizing resin containing 4.95 g of ethylene glycol phenyl ether acrylate and 4.95 g of 1,6-hexanediol diacrylate is added to a 20 mL scintillation vial. To the mixture, 0.1 g (1 wt %) photoinitiator, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, is added. The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. The second set of resin with slower kinetics, different thermodynamic miscibility, and an orthogonal polymerization mechanism were weighed out in a 20 mL scintillation vial and contained 4.9 g of epoxypropoxypropyl terminated polydimethylsiloxane, 8-11 cSt. In addition, a second photoinitiator and co-initiator, 0.05 g of triarylsulfonium hexafluoroantimonate salts, mixed and 0.05 g of isopropyl-thioxanthone, that initiates an orthogonal polymerization mechanism to the first set, was added. The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. The first and second resins were mixed in a weight ratio of 9:1. The mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s. The resin was used to print a custom designed structure using a stereolithographic printer (FIG. 27 a ). The final structure is washed three times in isopropanol by sonicating for about 10 min to remove residual resin, then UV cured for about 5 min to ensure complete polymerization. The phase separation results can be found in FIG. 31 where, as shown in panel a) of FIG. 31 the bottom of the structure is transparent and the top is dyed darker with the color of the second photoinitiator and co-initiator. Panel b) of FIG. 31 shows a Raman spectroscopy mapping, which shows the interface between the top and bottom of the structure with respect to the change in —C—H peak intensity relative to the baseline at ˜2920 cm⁻¹. 

1-79. (canceled)
 80. A method for making a product, the method comprising: a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition, and polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component; b) polymerizing at least one first polymerizable component to form at least one first polymer structure, and combining the at least one first polymer structure and at least one first component to form a composition, wherein the at least one first component comprises at least one functional component, at least one functional precursor component, or combinations thereof; or, c) combining at least one first polymerizable component and at least one polymer and/or polymer derivative to form a composition, and polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one polymer and/or polymer derivative, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
 81. The method of claim 80, wherein: part a) is performed and the at least one first polymer structure comprises at least one region having the at least one second polymerizable component, the at least one region having less of the at least one first polymer compared to the at least one second polymerizable component; part b) is performed and the at least one first polymer structure comprises at least one region having the at least one first component, the at least one region having less of the at least one first polymer compared to the at least one first component; or, part c) is performed and the at least one first polymer structure comprises at least one region having the at least one polymer and/or polymer derivative, the at least one region having less of the at least one first polymer compared to the at least one polymer and/or polymer derivative.
 82. The method of claim 80, wherein: part a) is performed and the at least one first polymer structure comprises at least one region having the at least one second polymerizable component, the at least one region having less of the at least one first polymer compared to the at least one second polymerizable component, and the at least one second polymerizable component is near, adjacent and/or coupled to the at least one first polymer structure; part b) is performed and the at least one first polymer structure comprises at least one region having the at least one first component, the at least one region having less of the at least one first polymer compared to the at least one first component, and the at least one first component is near, adjacent and/or coupled to the at least one first polymer structure; or, part c) is performed and the at least one first polymer structure comprises at least one region having the at least one polymer and/or polymer derivative, the at least one region having less of the at least one first polymer compared to the at least one polymer and/or polymer derivative, and the at least one polymer and/or polymer derivative is near, adjacent and/or coupled to the at least one first polymer structure.
 83. The method of claim 80, wherein: part a) is performed and the at least one second polymerizable component is polymerizable/polymerized whereby the at least one second polymerizable component reacts with the at least one first polymer to form at least one second polymer bonded/tethered to the at least one first polymer or the at least one second polymerizable component is polymerizable/polymerized to form the at least one second polymer, whereby the at least one second polymer reacts with the at least one first polymer to form a bond/tether therebetween; part b) is performed and the at least one first component reacts with the at least one first polymer to form at least one first component bonded/tethered to the at least one first polymer; or, part c) is performed and the at least one polymer and/or polymer derivative reacts with the at least one first polymer to form at least one polymer and/or polymer derivative bonded/tethered to the at least one first polymer.
 84. The method of claim 80, wherein part a) is performed and the method further comprises polymerizing the at least one second polymerizable component to form at least one second polymer.
 85. The method of claim 80, wherein part b) is performed and the at least one first component comprises at least one polymer and/or polymer derivative.
 86. The method of claim 80, wherein the at least one first polymer structure is a 3D-printed structure.
 87. The method of claim 86, wherein: part a) is performed and the 3D-printed structure has at least one region comprising the at least one second polymerizable component and/or an at least one second polymer formed by polymerizing the at least one second polymerizable component; part b) is performed and the 3D-printed structure has at least one region comprising the at least one first component; or, part c) is performed and the 3D-printed structure has the at least one polymer and/or polymer derivative.
 88. The method of claim 80, wherein the polymerizing comprises initiating polymerization in selected region(s) of the composition to form the at least one first polymer structure.
 89. The method of claim 80, wherein the polymerizing comprises initiating polymerization in selected region(s) of the composition to form the at least one first polymer and the unselected region(s) has the at least one second polymerizable component when part a) is performed, the at least one first component when part b) is performed, and/or the at least one polymer and/or polymer derivative when part c) is performed.
 90. The method of claim 80, wherein: part a) is performed and the at least one first polymerizable component and the at least one second polymerizable component are selectively irradiated at a wavelength such that one of the at least one first polymerizable component and the at least one second polymerizable component polymerize; part b) is performed and the at least one first polymerizable component and the at least one first component are selectively irradiated at a wavelength such that one of the at least one first polymerizable component and the at least one first component polymerizes; or, part c) is performed and the at least one first polymerizable component and the at least one polymer and/or polymer derivative are selectively irradiated at a wavelength such that one of the at least one first polymerizable component and the at least one polymer and/or polymer derivative polymerizes.
 91. The method of claim 90, wherein polymerized and unpolymerized regions are formed in the product.
 92. The method of claim 91, wherein the selectively irradiation comprises patterned irradiation, the patterned irradiation comprising one or more of direct writing application of light, interference, nanoimprint, diffraction gradient lithography, vat, volume, stereolithography, holography and digital light projection (DLP).
 93. The method of claim 92, wherein the method is 3D printing selected from the group consisting of vat polymerization, stereolithographic (SLA) printing, digital light processing (DLP) and volumetric 3D printing.
 94. The method of claim 90, wherein part a) is performed and the at least one first polymerizable component has at least one of an orthogonal polymerization mechanism, a rate of polymerization and a thermodynamic miscibility and the at least one second polymerizable component has at least one of an orthogonal polymerization mechanism, a rate of polymerization and a thermodynamic miscibility.
 95. The method of claim 94, wherein one or more of the orthogonal polymerization mechanism, rate of polymerization and thermodynamic miscibility is different between the at least one first polymerizable component and the at least one second polymerizable component.
 96. The method of claim 95, wherein the at least one second polymerizable component has one or more of a slower polymerization rate, slower orthogonal reactivity and lower solubility than the at least one first polymerizable component, and the at least one second polymerizable component diffuses towards non-irradiated region(s).
 97. The method of claim 80, wherein the composition is substantially homogeneous.
 98. The method of claim 90, wherein the method produces selective positioning of functionality in the product.
 99. The method of claim 80, wherein: part a) is performed and the at least two phases comprise an interface between a first phase and a second phase, wherein the interface has a concentration gradient of the at least one second polymerizable component, which decreases with distance away from the second phase towards the first phase, part b) is performed and at least two phases are formed from the at least one first polymer structure and the at least one first component and the at least two phases comprise an interface between a first phase and a second phase, wherein the interface has a concentration gradient of the at least one first component, which decreases with distance away from the second phase towards the first phase; or, part c) is performed and the at least two phases comprise an interface between a first phase and a second phase, wherein the interface has a concentration gradient of the at least one polymer and/or polymer derivative, which decreases with distance away from the second phase towards the first phase.
 100. The method of claim 99, wherein at least one of said at least two phases is a composite, a concentration gradient, a coating or a combination thereof.
 101. The method of claim 80, wherein: part a) is performed and one or both of the at least one first polymerizable component and the at least one second polymerizable component comprises one or more of at least one monomer, at least one oligomer and at least one resin; or, part b) is performed, the at least one first polymerizable component comprises one or more of at least one monomer, at least one oligomer or at least one resin, and the at least one first component comprises at least one functional monomer.
 102. The method of claim 101, wherein the at least one monomer comprises one or more of (meth)acrylate(s), acrylate(s), amine containing monomer(s) and epoxide containing monomer(s).
 103. The method of claim 101, wherein the at least one resin comprises one or more of at least one acrylate based-resin.
 104. A formulation comprising the composition formed in claim
 80. 105. A product produced by the method of claim
 80. 